WO2013008902A1

WO2013008902A1 - Composition for forming film

Info

Publication number: WO2013008902A1
Application number: PCT/JP2012/067878
Authority: WO
Inventors: Takahiko Sasaki; Tetsuji Yamaguchi
Original assignee: Dow Corning Toray Co., Ltd.
Priority date: 2011-07-11
Filing date: 2012-07-06
Publication date: 2013-01-17
Also published as: JP2013018860A

Abstract

A composition for forming a film comprising an activation energy beam curing resin (A) and oil-containing microparticles (B); a method for forming a film comprising applying the composition to a substrate surface and then irradiating the substrate surface with activation energy beams; and a substrate comprising a surface on which a film is formed via the method for forming a film. The composition can form a lubricating film on a substrate surface to provide the lubricating film having superior sliding durability, adhering excellently to a substrate, and having superior followability with regards to a deformation of the substrate.

Description

COMPOSITION FOR FORMING FILM TECHNICAL FIELD

[0001 ] The present invention relates to a composition for forming a film and a method for forming a film, and also relates to a method for manufacturing a surface coated substrate having a film formed on a surface thereof.

BACKGROUND ART

[0002] Forming a lubricating film on a substrate surface by applying a resin that can be cured by ultraviolet light or similar activation energy beams to various substrate surfaces, and irradiating using activation energy beams is known.

[0003] For example, Japanese Unexamined Patent Application Publication (Translation of PCT Application) No. 2005-513209A describes a composition for forming a lubricating film comprising a UV curable resin, in which said composition further comprises finely powdered polytetrafluoroethylene as a friction reducing agent. However, the lubricating film formed by such a composition creates a state of boundary lubrication upon contact with an object and, therefore the coefficient of friction increases and the lubricating film tends to peel off, leading to inferior sliding durability. If the compounded amount of the finely powdered

polytetrafluoroethylene is increased to compensate for this, the UV curing properties will tend to deteriorate and adhesion between the lubricating film and the substrate will tend to deteriorate.

[0004] Japanese Unexamined Patent Application Publication No. 2004-176054A and Japanese Unexamined Patent Application Publication No. 201 1 -26606A describe a

composition for forming a lubricating film comprising a UV curable resin and silicone oil or a similar lubricating agent. However in cases where, for example, a low molecular weight siloxane included in the composition is deposited as silica at an electric contact via pyrolysis, problems occur such as contact failure and the like.

[0005] On the other hand, Japanese Unexamined Patent Application Publication No. 2002-69473A and Japanese Unexamined Patent Application Publication No. 2003-73609A describe a thermal curing composition for forming a lubricating film wherein microcapsules in which a capsule wall is formed from urea resin, melamine resin, or the like, the microcapsules encapsulating an oil or a grease, are compounded in a thermal curing resin. However, the film obtained using such a thermal curing composition for forming a lubricating film has insufficient sliding durability. Additionally, adhesion to a substrate is poor and it is difficult for said film to follow deformations when the substrate deforms. Moreover, because heating is necessary in the film forming, there is a problem in that a film cannot be formed on substrates that are formed from thermoplastic resins, rubbers, and similar materials having low heat resistance properties.

[0006] Additionally, Japanese Unexamined Patent Application Publication (Translation of

PCT Application) No. 2005-513257A describes a sealing element in which microcapsules are dispersed, said microcapsules comprising a lubricant encapsulated in a polymer matrix formed from polyetheretherketone or a similar plastic. Japanese Unexamined Patent Application Publication No. 2007-131676A describes a composition for a lubricating film comprising microcapsules in which a volatile organic solvent, a binder, and a lubricant are encapsulated.

However, these documents do not recite or suggest the use of a resin that is cured by ultraviolet light or similar activation energy beams.

PRIOR ART DOCUMENTS

Patent Documents

[0007] Patent Document 1 : Japanese Unexamined Patent Application Publication

(Translation of PCT Application) No. 2005-513209A

Patent Document 2: Japanese Unexamined Patent Application Publication No. 2004-176054A Patent Document 3: Japanese Unexamined Patent Application Publication No. 2011-26606A Patent Document 4: Japanese Unexamined Patent Application Publication No. 2002-69473A Patent Document 5: Japanese Unexamined Patent Application Publication No. 2003-73609A Patent Document 6: Japanese Unexamined Patent Application Publication (Translation of PCT Application) No. 2005-513257A

Patent Document 7: Japanese Unexamined Patent Application Publication No. 2007-131676A

SUMMARY OF INVENTION

[0008] In light of the conventional art described above, an object of the present invention is to provide a composition that can form on a surface of a substrate made from an arbitrary material, the lubricating film having superior sliding durability, adhering excellently to a substrate, and having superior followability with regards to a deformation in cases when the substrate deforms; and a method for forming the film. Another object of the present invention is to provide a substrate having the superior characteristics described above.

[0009] The object of the present invention is achieved by a composition for forming a film comprising an activation energy beam curing resin (A) and oil-containing microparticles (B).

[0010] The activation energy beams are preferably ultraviolet light.

[0011] The activation energy beam curing resin (A) is preferably radical-polymerizable.

[0012] The composition for forming a film of the present invention preferably further comprises an activation energy beam polymerization initiator (C). In this case, from 0.1 to 10 parts by weight (mass) of the activation energy beam polymerization initiator (C) is preferably compounded per 100 parts by weight (mass) of the activation energy beam curing resin (A) in the composition for forming a film.

[0013] The oil-containing microparticles (B) preferably are microcapsules comprising a capsule wall encapsulating at least one type of oil.

[0014] The oil is preferably a fluorinated oil.

[0015] The capsule wall can be formed from at least one type of thermosetting resin.

[0016] A diameter of the oil-containing microparticles (B) is preferably in a range from 1 to 30 Mm.

[001 ] The oil can account for 20 to 90 wt.% (mass%) of a total weight (mass) of the oil-containing microparticles (B).

[0018] A range of 1 to 100 parts by weight (mass) of the oil-containing microparticles (B) can be compounded per 100 parts by weight (mass) of the activation energy beam curing resin (A) in the composition for forming a film.

[0019] The composition for forming a film of the present invention may further comprise at least one type of inorganic microparticles and/or organic microparticles (D).

[0020] The composition for forming a film of the present invention may further comprise at least one type of solvent (E).

[0021] The present invention also relates to a method for forming a film comprising applying the composition for forming a film described above to a substrate surface, and then irradiating the substrate surface with activation energy beams; and also to a substrate comprising a surface on which a film is formed via said method for forming a film.

[0022] Additionally, the present invention also relates to a method for manufacturing a surface coated substrate comprising a step of applying the composition for forming a film described above to a substrate surface, and then irradiating the substrate surface with activation energy beams.

[0023] With the composition for forming a film and the method for forming a film of the present invention, a lubricating film whereby excellent sliding characteristics can be maintained over an extended period of time and that has superior sliding durability can be formed on a substrate.

[0024] Additionally, with the composition for forming a film and the method for forming a film of the present invention, a film can be formed on a substrate, the film bonding excellently with the substrate, and having superior followability with regards to a deformation in cases when the substrate deforms.

[0025] Moreover, with the composition for forming a film and the method for forming a film of the present invention, the film can be formed on the surface of a substrate made from an arbitrary material because heating is not necessary.

[0026] Thus, the film obtained via the present invention has superior sliding durability, bonds excellently with the substrate, has superior followability with regards to a deformation in cases when the substrate deforms and, moreover, can be formed on any type of substrate.

[0027] The substrate of the present invention comprises a surface having lubricity and superior sliding durability and, therefore, the substrate can be in contact with another arbitrary object for extended periods of time, and is suitable as a sliding member that is in contact with and moves relative to another object.

DETAILED DESCRIPTION OF THE INVENTION

[0028] The composition for forming a film of the present invention comprises essentially: an activation energy beam curing resin (A), and

oil-containing microparticles (B).

In the present invention, "activation energy beams" refers to electromagnetic waves and corpuscular beams such as infrared rays, visible light, ultraviolet light, x-rays, electron rays, radiation beams, and the like, of which ultraviolet light having a wavelength of 180 to 500 nm and preferably from 200 to 450 nm is preferable.

[0029] The activation energy beam curing resin (A) is not particularly limited, provided that it is a resin that can be polymerized and cured by irradiation with activation energy beams but, due to being curable over a short period of time, having low heat generation when curing, and being able to suppress impact on the substrate, the activation energy beam curing resin (A) is preferably radical-polymerizable. Examples of the activation energy beam curing resin (A) include urethane resins, olefin resins, epoxy resins, polyamideimide resins, and acrylic resins that have an acrylate group or a methacrylate group, or modified products thereof; and also mixtures thereof.

[0030] The activation energy beam curing resin (A) preferably is a resin composition comprising at least one type of compound that initiates a polymerization reaction by irradiation with activation energy beams. The compound that initiates the polymerization reaction by irradiation with activation energy beams preferably is a polyfunctional compound having two or more polymerizable functional groups capable of being polymerized by activation energy beams in each molecule. Examples of the polymerizable functional groups include acryloyl groups, methacryloyl groups, vinyl groups, allyl groups, and similar groups having

carbon-carbon double bonds. Of these, acryloyl groups or methacryloyl groups are preferable and, from the point of polymerizability, acryloyl groups are more preferable. Note that the polyfunctional compound may have a total of two or more of two or more types of polymerizable functional groups in each molecule. A range of the number of polymerizable functional groups in each molecule of the polyfunctional compound is not particularly limited but, normally, from 2 to 50 groups is suitable, but from 2 to 30 groups is preferable.

[0031] In a preferable aspect, the activation energy beam curing resin (A) comprises at least a polyfunctional compound (hereinafter also referred to as "polyfunctional compound (a-1)") having two or more of one or more type of polymerizable functional group selected from acryloyl groups and methacryloyl groups. Note that in the descriptions given below, the acryloyl groups and the methacryloyl groups are referred to collectively as "(meth)acryloyl groups".

[0032] The polyfunctional compound (a-1) may have various functional groups or bonds in addition to the polymerizable functional groups. Examples thereof include hydroxyl groups, carboxyl groups, halogen atoms, epoxy groups, urethane bonds, ether bonds, ester bonds, carbonate bonds, thioether bonds, amide bonds, imide bonds, and the like. A (meth)acryloyl group-containing compound having urethane bonds and a (meth)acrylic ester compound free of urethane bonds are particularly preferable as the polyfunctional compound (a-1). These two polyfunctional compounds will be described hereinafter.

[0033] Examples of the (meth)acryloyl group-containing compound having urethane bonds (hereinafter referred to as "acrylic urethane") include:

(1) a reaction product of a compound having (meth)acryloyl groups and hydroxyl groups (a1) and a compound having two or more isocyanate groups (hereinafter referred to as "polyisocyanate");

(2) a reaction product of the compound (a1), a compound having two or more hydroxyl groups (a2), and the polyisocyanate;

(3) a reaction product of a compound having (meth)acryloyl groups and isocyanate groups (a3) and the compound (a2); and the like.

[0034] These reaction products are preferably free of isocyanate groups, but may include hydroxyl groups. Thus, in the production of these reaction products, a total number of moles of the hydroxyl groups of the total reactant is preferably greater than or equal to a total number of moles of the isocyanate groups.

[0035] The compound (a1) having the (meth)acryloyl groups and the hydroxyl groups may be a compound having one each of the (meth)acryloyl group and the hydroxyl group. The compound (a1) may alternately be a compound having two or more of the (meth)acryloyl groups and one of the hydroxyl groups, a compound having one of the (meth)acryloyl groups and two or more of the hydroxyl groups, or a compound having two or more of each of the (meth)acryloyl groups and the hydroxyl groups.

[0036] Specific examples thereof include, in the order described above,

2-hydroxyethyl(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane mono(meth)acrylate, pentaerythritol di(meth)acrylate, and a reaction product of 2-hydroxyethyl (meth)acrylate and neopentylglycol carbonate, or the like. These are monoesters of a compound having two or more hydroxyl groups and a (meth)acrylate, or polyesters having one or more hydroxyl group remaining.

[0037] Furthermore, the compound (a1) may be a ring-opening reaction product of a compound having one or more epoxy group and (meth)acrylate. Ester bonds and hydroxyl groups are generated via the opening of the epoxy groups through the reaction of the epoxy groups with the (meth)acrylate, and result in a compound having (meth)acryloyl groups and hydroxy! groups. Additionally, a hydroxyl group-containing compound can be obtained by opening the epoxy groups of the compound having one or more epoxy group, and this compound can be converted into a (meth)acrylic ester.

[0038] The compound having one or more epoxy group is preferably the polyepoxide known as epoxy resin. Preferable examples of the polyepoxide include a compound having two or more glycidyl groups such as a polyhydric phenol-polyglycidylether (e.g. a bisphenol

A-diglycidylether), and an alicyclic epoxy compound. Furthermore, a reaction product of a (meth)acrylate having epoxy groups and a compound having hydroxyl groups and carboxyl groups can be used as the compound (a1). Examples of the (meth)acrylate having epoxy groups include glycidyl (meth)acrylate.

[0039] Specific examples of the compound (a1) other than those described above include 2-hydroxypropyl (meth)acrylate, 1 ,3-propanediol mono(meth)acrylate, 1 ,4-butanediol mono(meth)acrylate, 2-butene-1 ,4-diol mono(meth)acrylate, 1 ,6-hexanediol

mono(meth)acrylate, glycidol di(meth)acrylate, pentaerythritol tri(meth)acrylate,

dipentaerythritol mono(to penta)(meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, a reaction product of bisphenol A-diglycidylether and (meth)acrylic acid, and the like.

[0040] The polyisocyanate may, of course, be an ordinary monomeric polyisocyanate, but may also be a polyisocyanate multimer or variant, or a prepolymeric compound such as an isocyanate group-containing urethane prepolymer, or the like.

[0041] Examples of the multimer include trimers (isocyanurate variant), dimers, carbodiimide variants, and the like. Examples of the variants include urethane variants, biuret variants, allophanate variants, urea variants, and the like that are obtained by modifying using trimethylolpropane and other polyhydroxy alcohols. Examples of prepolymeric compounds include isocyanate group-containing urethane prepolymers and the like obtained by reacting a polyether polyol, a polyester polyol, or a similar polyol with a polyisocyanate. Combinations of two or more types of the polyisocyanate can be used.

[0042] Specific examples of the monomeric polyisocyanate include 2,6-tolylene diisocyanate, 2,4-tolylene diisocyanate, methylene bis(4-phenyl isocyanate) [MDI], 1 ,5-naphthalene diisocyanate, tolidine diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, p-phenylene diisocyanate, transcyclohexane-1 ,4-diisocyanate, xylylene diisocyanate [XDI], hydrogenated XDI, hydrogenated MDI, lysine diisocyanate, tetramethylxylene diisocyanate, trimethylhexamethylene diisocyanate, lysine ester triisocyanate, 1 ,6,11-undecane triisocyanate, 1 ,8-diisocyanate-4-isocyanate methyloctane, 1 ,3,6-hexamethylene triisocyanate,

bicycloheptane triisocyanate, and the like (abbreviations are included in brackets).

[0043] Non-yellowing polyisocyanate (polyisocyanate free of isocyanate groups directly bonded to aromatic nuclei) is particularly preferable as the polyisocyanate. Specific examples thereof include hexamethylene diisocyanate and similar aliphatic polyisocyanates, isophorone diisocyanate and similar alicyclic polyisocyanates, and xylylene diisocyanate and similar aromatic polyisocyanates. As described above, multimers and variants of the polyisocyanate are also preferable.

[0044] Examples of the compound (a2) having two or more hydroxyl groups include polyhydroxy alcohols, polyols with a higher molecular weight compared to polyhydroxy alcohols, and the like. The polyhydroxy alcohol is preferably a polyhydroxy alcohol having from 2 to 8 hydroxyl groups, and is more preferably a polyhydroxy alcohol having from 2 to 6 hydroxyl groups. The polyhydroxy alcohol may, of course, be an aliphatic polyhydroxy alcohol, and may also be a polyhydroxy alcohol having an alicyclic polyhydroxy alcohol and an aromatic nucleus.

[0045] Examples of the polyhydroxy alcohol having an aromatic nucleus include alkylene oxide adducts of polyhydric phenols, ring-opened products of polyepoxides having an aromatic nucleus such as polyhydric phenol-polyglycidylether or the like, and the like. Examples of the polyol having a high molecular weight include polyether polyols, polyester polyols, polyetherester polyols, polycarbonate polyols, and the like. Additionally, a hydroxyl group-containing vinyl polymer can also be used as the polyol. Combinations of two or more types of the polyhydroxy alcohol and the polyol can also be used.

[0046] Specific examples of the polyhydroxy alcohol include ethylene glycol, 1 ,2-propylene glycol, 1 ,3-propanediol, 1 ,3-butanediol, 1 ,4-butanediol, 1 ,6-hexanediol, diethyleneglycol, dipropylene glycol, neopentyl glycol, 2,2,4-trimethyl-1 ,3-pentanediol, cyclohexanediol, dimethylol cyclohexane, trimethylolpropane, glycerin, tris(hydroxyalkyl)isocyanurate, pentaerythritol, ditrimethylolpropane, dipentaerythritol,

3,9-bis(hydroxymethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane,

3,9-bis(2-hydroxy-1 , 1 -dimethylethyl)-2,4,8, 10-tetraoxaspiro[5.5]undecane, ring-opened products of bisphenol A-diglycidylether, ring-opened products of vinyl cyclohexene dioxide, and the like.

[0047] Specific examples of the polyol include polyethyleneglycol, polypropylene glycol, bisphenol A-alkylene oxide adducts, polytetramethyleneglycol, and similar polyether polyols; polybutadiene diol, hydrogenated polybutadiene diol, and similar aliphatic polyols; poly ε-caprolactone polyol; polyester polyols obtained by reacting adipic acid, sebacic acid, phthalic acid, maleic acid, fumaric acid, azelaic acid, glutaric acid, or a similar polybasic acid with the polyhydroxy alcohol described above; polycarbonate diols obtained by reacting 1 ,6-hexanediol or a similar diol with carbonate ester or phosgene; and the like.

[0048] Examples of the hydroxyl group-containing vinyl polymer include copolymers of allyl alcohol, vinyl alcohol, hydroxy alkyl vinyl ether, hydroxyalkyl (meth)acrylate, or a similar hydroxyl group-containing monomer and olefin or a similar hydroxyl group-free monomer, and the like.

[0049] Examples of the compound (a3) having the (meth)acryloyl groups and the isocyanate groups include 2-isocyanatoethyl (meth)acrylate, methacryloyl isocyanate, and the like.

[0050] Preferable examples of the acrylic urethane include an acrylic urethane (hereinafter referred to as "pentaerythritol-based acrylic urethane") obtained by using a polyester having one or more hydroxyl groups of pentaerythritol or polypentaerythritol and (meth)acrylic acid remaining (hereinafter referred to as "hydroxyl group-containing pentaerythritol-based

(meth)acrylate"). Reaction products of the hydroxyl group-containing pentaerythritol-based (meth)acrylate and the polyisocyanate; reaction products obtained by reacting the

polyisocyanate with a mixture of the hydroxyl group-containing pentaerythritol-based

(meth)acrylate and the compound (a2), or the like, having two or more other hydroxyl groups at a relatively lower amount; and the like are particularly preferable.

[0051] The polypentaerythritol may be a mixture of polypentaerythritols having different degrees of polymerization, and may include pentaerythritol. Likewise, the hydroxyl group-containing pentaerythritol-based (meth)acrylate may be a mixture of two or more types of compounds such as a mixture of two or more types of compounds derived from the

polypentaerythritol described above; or a mixture of two or more types of differing compounds having hydroxyl groups and (meth)acryloyloxy groups in each molecule. The same holds for the pentaerythritol-based acrylic urethane.

[0052] Furthermore, examples of preferable acrylic urethanes also include polyester-based polyurethanes obtained using a polyester polyol. Reaction products of the compound (a1) having the (meth)acryloyl groups and the hydroxyl groups, polyester polyol, and

polyisocyanate; and reaction products obtained by reacting polyisocyanate with a mixture of the compound (a1) having the (meth)acryloyl groups and the hydroxyl groups, polyester polyol, and the compound (a2) having two or more other hydroxyl groups at a relatively lower amount with respect to the polyester polyol; and the like are particularly preferable.

[0053] Additionally, polycarbonate-based polyurethanes obtained by using polycarbonate diol are also preferable. Reaction products of the compound (a1) having the (meth)acryloyl groups and the hydroxyl groups, polycarbonate diol, and polyisocyanate; and reaction products obtained by reacting polyisocyanate with a mixture of the compound (a1) having the (meth)acryloyl groups and the hydroxyl groups, polycarbonate diol, and the compound (a2) having two or more other hydroxyl groups at a relatively lower amount with respect to the polycarbonate diol; and the like are particularly preferable.

[0054] A polyester obtained by reacting a compound like the compound (a2) having two or more hydroxyl groups with (meth)acrylic acid is preferable as the (meth)acrylic ester compound free of urethane bonds. The polyhydroxy alcohol and polyol described above is preferable as the compound having two or more hydroxyl groups. Furthermore, a (meth)acrylic ester compound, which is a reaction product of a compound having two or more epoxy groups and (meth)acrylic acid is also preferable.

[0055] The polyepoxide known as epoxy resin can be used as the compound having two or more epoxy groups. For example, commercially available products such as glycidyl ether polyepoxide, alicyclic polyepoxide, and similar epoxy resins can be used as the polyepoxide.

[0056] Specific examples of the polyepoxide include bisphenol A-diglycidylether, bisphenol F-diglycidylether, tetrabromobisphenol A-diglycidylether, glycerin triglycidylether, novolac polyglycidylether, vinyl cyclohexene dioxide, dicyclopentadiene dioxide, and the like.

[0057] Specific examples of the (meth)acrylic ester compound free of urethane bonds include the compounds described below.

[0058] 1 ,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1 ,6-hexanediol di(meth)acrylate, a di(meth)acrylate of long chain aliphatic diol having from 14 to 15 carbons, 1 ,3-butanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol

di(meth)acrylate, glycerol tri(meth)acrylate, glycerol di(meth)acrylate, triglycerol

di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipenta erythritol hexa(meth)acrylate, dipenta erythritol penta(meth)acrylate, a di(meth)acrylate of a diol formed from a condensate of neopentyl glycol and trimethylolpropane, and similar (meth)acrylates of aliphatic polyhydroxy alcohol. [0059] Di(2-(meth)acryloyloxyethyl)bisphenol A, di(2-(meth)acryloyloxyethyl)bisphenol S, di(2-(meth)acryloyloxyethyl)bisphenol F, tris(2-(meth)acryloyloxyethyl)isocyanurate, bis(2-(meth)acryloyloxyethyl)-(2-hydroxyethyl)isocyanurate, bisphenol A dimethacrylate, and similar (meth)acrylates of polyhydroxy alcohols or polyhydric phenols having an aromatic nucleus or a triazine ring.

[0060] A tri(rrieth)acrylate of a trimethylolpropane-ethylene oxide adduct, a tri(meth)acrylate of a trimethylolpropane-propylene oxide adduct, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, a hexa(meth)acrylate of a dipenta erythritol-caprolactone adduct, a tri(meth)acrylate of a

tris(2-hydroxyethyl)isocyanurate-caprolactone adduct, polyethyleneglycol [200 to 1000] di(meth)acrylate, polypropylene glycol [200 to 1000] di(meth)acrylate, and similar

(meth)acrylates of hydroxyl group-containing compound-alkylene oxide adducts,

(meth)acrylates of hydroxyl group-containing compound-caprolactone adducts, and

(meth)acrylates of polyoxyalkylene polyols (ranges in the brackets indicate the molecular weight of the polyoxyalkylene polyol).

[0061] Bis(acryloyloxy neopentyl glycol)adipate, a di(meth)acrylate of a neopentylglycol hydroxypivalate ester, a di(meth)acrylate of a neopentylglycol hydroxypivalate

ester-caprolactone adduct, bis(2-(meth)acryloyloxyethyl)phosphate,

tris(2-(meta)acryloyloxyethyl)phosphate, and similar carboxylate esters and phosphate esters having (meth)acryloyl groups.

[0062] A (meth)acrylic acid adduct of a bisphenol A-diglycidylether, vinylcyclohexene dioxide-(meth)acrylic acid adduct, dicyclopentadiene dioxide-(meth)acrylic acid adduct, a reaction product of glycidyl (meth)acrylate and ethylene glycol, a reaction product of glycidyl (meth)acrylate and propylene glycol, a reaction product of glycidyl (meth)acrylate and diethyleneglycol, a reaction product of glycidyl (meth)acrylate and 1 ,6-hexanediol, a reaction product of glycidyl (meth)acrylate and glycerol, a reaction product of glycidyl (meth)acrylate and trimethylolpropane, a reaction product of glycidyl (meth)acrylate and phthalic acid, and similar (meth)acrylic acid adducts of polyepoxides (however, one molecule of (meth)acrylic acid is added per one epoxy group of the polyepoxide), and a reaction product of glycidyl

(meth)acrylate and polyhydroxy alcohol or polyhydric carboxylic acid (however, two or more molecules of the glycidyl (meth)acrylate are reacted per one molecule of the polyhydroxy alcohol) and the like.

[0063] Alkyl-modified dipentaerythritol penta(meth)acrylate, alkyl-modified dipentaerythritol tetra(meth)acrylate, alkyl-modified dipenta erythritol tri(meth)acrylate, an allyl-etherified product of a vinylcyclohexene dioxide-(meth)acrylic acid adduct, a methyl-etherified product of a vinylcyclohexene dioxide-(meth)acrylic acid adduct, ,or a carboxylic acid-esterified product, alkenyl-etherified product, or alkyl-etherified product of a (meth)acrylate like those described above that having unreacted hydroxyl groups such as a stearic acid-modified pentaerythritol di(meth)acrylate.

[0064] A particularly preferable (meth)acrylic ester compound free of urethane bonds is a poly(meth)acrylate of an isocyanurate-based polyol (hereinafter referred to as

"isocyanurate-based (meth)acrylate"). The isocyanurate-based polyol is an isocyanuric acid ester having two or more hydroxyl groups such as tris(hydroxyalkyl)isocyanurate or the like. In the isocyanurate-based polyol, the three organic groups bonded, respectively, to the three nitrogen atoms of the isocyanurate ring may be the same or different. Each of at least two of the three organic groups preferably has at least one hydroxyl group and, more preferably, each of the three organic groups has one hydroxyl group.

[0065] Other than tris(hydroxyalkyl)isocyanurate, a tris(hydroxyalkyl)isocyanurate-alkylene oxide adduct and a tris(hydroxyalkyl)isocyanurate-lactone adduct are preferable as the isocyanurate-based polyol. An added amount of alkylene oxide or lactone in these adducts is preferably from 1 to 12 molecules and more preferably from 1 to 6 molecules per one molecule of the tris(hydroxyalkyl)isocyanurate. A hydroxyalkyl group having from 2 to 6 and more preferably from 2 to 4 carbons is preferable as the hydroxyalkyl group in the

tris(hydroxyalkyl)isocyanurate. Specific examples thereof include a 2-hydroxyethyl group, a 2-hydroxypropyl group, a 4-hydroxybutyl group, and the like. Preferable examples thereof are the 2-hydroxyethyl group and the 2-hydroxypropyl group. Note that combinations of two or more types of these isocyanurate-based polyols can be used.

[0066] Ethylene oxide, propylene oxide, 1 ,2-butene oxide, 2,3-butene oxide, and the like are preferable as the alkylene oxide, of which ethylene oxide and propylene oxide are more preferable. Other than ε-caprolactone, butyrolactone, γ-valerolactone, γ-caprolactone, δ-caprolactone, and the like are preferable as the lactone, of which ε-caprolactone is particularly preferable.

[0067] An appropriate number of (meth)acryloyloxy groups per one molecule of the isocyanurate-based (meth)acrylate is from 2 to 3, and these may be a mixture. Preferably, the isocyanurate-based (meth)acrylate has three (meth)acryloyloxy groups. Preferable examples of the isocyanurate-based (meth)acrylate include those compounds described above, as well as tris(2-(meth)acryloyloxyethyl)isocyanurate,

bis(2-(meth)acryloyloxyethyl)-(2-hydroxyethyl)isocyanurate, a tri(meth)acrylate or

di(meth)acrylate of a triol formed from a ε-caprolactone 1 to 3 molecular adduct of

tris(2-hydroxyethyl)isocyanurate, a tri(meth)acrylate or di(meth)acrylate of a triol formed from an ethylene oxide 1 to 3 molecular adduct of tris(2-hydroxyethyl)isocyanurate, and the like.

[0068] Compounds that are particularly preferable as the polyfunctional compound (a-1) are the pentaerythritol-based acrylic urethane and the isocyanurate-based (meth)acrylate, which were described above. These may also be preferably used in combination. A ratio that these account for in the entire polyfunctional compound (a-1) is preferably not less than 20 wt.% (mass%), and more preferably not less than 40 wt.% (mass%).

[0069] The activation energy beam curing resin (A) may further comprise another polymerizable compound such as a monofunctional compound (hereinafter referred to as "monofunctional compound (a-2)"), or the like.

[0070] A monofunctional polymerizable compound having one (meth)acryloyl group in each molecule is preferable as the monofunctional compound (a-2). Examples of the

monofunctional compound (a-2) include the following compounds expressed by the general formula CH₂=C(R¹)COOC_zH_2z+1 (wherein, R¹ is a hydrogen atom or a methyl group, z is an integer from 1 to 13, and C_zH_2z+1 may be a straight chain structure or a branched chain structure): alkyl(meth)acrylate, allyl(meth)acrylate, benzyl(meth)acrylate,

butoxyethyl(meth)acrylate, butanediol(meth)acrylate, butoxy triethylene glycol

mono(meth)acrylate, tert-butylaminoethyl(meth)acrylate,

3-chloro-2-hydroxypropyl(meth)acrylate, 2-cyanoethyl(meth)acrylate, cyclohexyl(meth)acrylate, 2,3-dibromopropyl(meth)acrylate, dicyclopentenyl(meth)acrylate,

N,N-diethylaminoethyl(meth)acrylate, N,N-dimethylaminoethyl(meth)acrylate, 2-ethoxy ethyl(meth)acrylate, 2-(2-ethoxy ethoxy)ethyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, glycerol(meth)acrylate, glycidyl (meth)acrylate, heptadecafluorodecyl(meth)acrylate,

2-hydroxyethyl(meth)acrylate, 2-hydroxy-3-(meth) acryloyloxypropyl trimethyl ammonium chloride, 2-hydroxypropyl(meth)acrylate, Y-(meth)acryloxypropyl trimethoxysilane,

2-methoxyethyl(meth)acrylate, methoxy diethylene glycol(meth)acrylate, methoxy triethylene glycol(meth)acrylate, methoxy tetraethylene glycol(meth)acrylate, methoxy dipropylene glycol(meth)acrylate, methoxylated cyclodecatriene(meth)acrylate, morpholine(meth)acrylate, nonylphenoxy polyethyleneglycol(meth)acrylate, nonylphenoxy polypropylene

glycol(meth)acrylate, octafluoropentyl(meth)acrylate, phenoxy hydroxypropyl(meth)acrylate, phenoxy ethyl(meth)acrylate, phenoxy diethyleneglycol(meth)acrylate, phenoxy tetra ethylene glycol(meth)acrylate, phenoxy hexa ethylene glycol(meth)acrylate, phenoxy(meth)acrylate, polypropylene glycol(meth)acrylate, 2-sulfonic acid sodium ethoxy (meth)acrylate,

tetrafluoropropyl(meth)acrylate, tetrahydrofurfuryl(meth)acrylate, trifluoroethyl(meth)acrylate, vinyl acetate, N-vinylcaprolactam, N-vinylpyrrolidone, dicyclopentadienyl(meth)acrylate, isobornyl acrylate, and the like.

[0071] The polyfunctional compound (a-1) can account for 20 to 100 wt.% (mass%), preferably 50 to 100 wt.% (mass%), and more preferably 70 to 100 wt.% (mass%) of the total weight (mass) of the polymerizable compound included in the activation energy beam curing resin (A). When the ratio of the polyfunctional compound (a-1 ) of the polymerizable monomers included in the activation energy beam curing resin (A) is within the range described above, the wear resistance of the film formed from a cured product of the composition for forming a film of the present invention will be particularly superior.

[0072] The oil-containing microparticles (B) are not particularly limited, provided that they are microparticles that contain an oil and, in general, preferably have a median diameter

(measurement using a laser diffraction/scattering type particle size distribution) of 0.1 to 50 μηη, more preferably of 1 to 30 pm, and even more preferably of 1 to 20 μηι. The size of the oil-containing microparticles (B) can be appropriately selected depending on film thickness when the composition for forming a film of the present invention is applied to a substrate.

[0073] The oil-containing microparticles (B) preferably are microcapsules comprising a capsule wall encapsulating at least one type of oil. Oil is encapsulated in the hollow portion surrounded by the capsule wall of the microcapsules and exists as an oil-containing bubble in the composition for forming a film of the present invention. When the microcapsules break, the oil coats the substrate surface and, thereby increases the lubricity of said surface. A form of the microcapsules is not particularly limited and may be a spherical or disc-like shape.

Additionally, a structure of the capsule wall is not particularly limited, and a hole, groove, or the like may be present in a portion of the capsule wall. Moreover, the oil may not be completely enclosed by the capsule wall.

[0074] The material of the capsule wall of the microcapsules is not particularly limited, but is preferably formed from at least one type of thermosetting resin. Combinations of two or more types of thermosetting resins may also be used. In cases where a single thermosetting resin is used, there is a greater tendency for a groove or hole to be formed in the capsule wall, and there may be difficulties in encapsulating and sealing the oil in the capsule. In cases where two or more types of thermosetting resins are used, it is difficult to form a groove or hole and, therefore, it is easy to encapsulate and seal the oil in the capsule, and microcapsules can be formed that have superior liquid tightness. When the liquid tightness of the microcapsules is superior, leaking of the oil from the microcapsules in the composition for forming a film of the present invention can be prevented. Moreover, it is possible to break the microcapsules and discharge the oil via friction with other members at the substrate surface and, therefore, excellent friction characteristics can be maintained over an extended period of time.

[0075] A urea resin, a melamine resin, an urea-formalin resin, a urethane resin, a benzoguanamine resin, or a similar nitrogen-containing resin is preferable as the thermosetting resin. Urea resins have heat resistance properties and have a high degree of hardness. Melamine resins have superior resistance to impacts, and also have heat resistance properties and superior flame resistance properties. Benzoguanamine resins have cracking resistance improved over that of melamine resins. A capsule wall having superior characteristics can be easily formed using a mixture of these resins. In this case, a more preferable compounding ratio (weight (mass) ratio) of the mixed resins is such that urea resin:melamine resin is from 3:7 to 7:3. When the compounding ratio is within this range, compared to cases when it is outside this range, a capsule wall having a higher degree of hermeticity can be formed.

[0076] Any type of oil can be used as the oil encapsulated in the microcapsules, provided that it has lubricity, and a kinetic viscosity thereof is preferably in a range from 10 to 1 ,000 mm²/s.

[0077] The oil is preferably at least one type selected from the group consisting of silicone-based oil agents and non-silicone-based organic oil agents, and the types and viscosities of these oil agents can be appropriately selected depending on the use and the like thereof. [0078] In general, silicone-based oil agents are hydrophobic, and a molecular structure thereof may be straight, cyclic, or branched. In general, the functional groups of

silicone-based oil agents are methyl groups or hydroxyl groups. The silicone-based oil agent may be an organo-modified silicone having a portion or all of said functional groups substituted by organo-modified groups. The backbone of these organo-modified silicones, in addition to polysiloxane bonds, may include an alkylene chain, an aminoalkylene chain, or a polyether chain; and may include a so-called "block copolymer". Additionally, the organo-modified groups may be included in a sidechain or one or both terminals of a polysiloxane chain.

Specific examples thereof include amino-modified silicone, aminopolyether-modified silicone, epoxy-modified silicone, carboxyl-modified silicone, amino acid-modified silicone,

acryl-modified silicone, phenol-modified silicone, amidealkyl-modified silicone,

polyamide-modified silicone, aminoglycol-modified silicone, alkoxy-modified silicone, silicone modified by higher alkyl having from 8 to 30 carbons, and alkyl-modified silicone resin.

[0079] The organic oil agent is exemplified by higher alcohols, hydrocarbon oils, ester oils, higher fatty acids, and fluorinated oils and, in the present invention, is not particularly limited, but fluorinated oils are preferable. With a fluorinated oil, not only can excellent sliding characteristics be obtained, but, compared with other oils, impact on plastic substrates, particularly the generation of solvent cracking, is small.

[0080] The higher alcohol is, for example, a higher alcohol having from 10 to 30 carbons. Said higher alcohol is a saturated or unsaturated monovalent aliphatic alcohol, and the hydrocarbon group portion thereof may be straight or branched, but is preferably straight. Examples of the higher alcohols having from 10 to 30 carbons include lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, behenyl alcohol, hexadecyl alcohol, oleyl alcohol, isostearyl alcohol, hexyldodecanol, octyldodecanol, cetostearyl alcohol, 2-decyltetradecinol, cholesterol, sitosterol, phytosterol, lanosterol, lanolin alcohol, hydrogenated lanolin alcohol, and the like. Note that in the present invention, it is preferable that a single higher alcohol having a melting point from 40 to 80°C is used or, alternately that a plurality of higher alcohols is combined so that a melting point thereof is from 40 to 70°C. The higher alcohols described above act with a surfactant to form an aggregate known as an "alpha gel", increase the viscosity of the formulation, and stabilize emulsions and, therefore are particularly useful as the base ingredient of a hair cosmetic composition.

[0081] Examples of the hydrocarbon oil include liquid paraffin, light liquid isoparaffin, heavy liquid isoparaffin, vaseline, n-paraffin, isoparaffin, isododecane, isohexadecane,

polyisobutylene, hydrogenated polyisobutylene, polybutene, ozokerite, ceresin, microcrystalline wax, paraffin wax, polyethylene wax, polyethylene/polypropylene wax, squalane, squalene, pristane, polyisoprene, and the like.

[0082] Examples of the ester oil include hexyldecyl octanoate, cetyl octanoate, isopropyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, oleyl oleate, decyl oleate, octyldodecyl myristate, hexyldecyl dimethyloctanoate, cetyl lactate, myristyl lactate, diethyl phthalate, dibutyl phthalate, lanolin acetate, ethylene glycol monostearate, propylene glycol monostearate, propylene glycol dioleate, glyceryl monostearate, glyceryl monooleate, glyceryl tri-2-ethylhexanoate, trimethylolpropane tri-2-ethylhexanoate,

ditrimethylolpropane triethylhexanoate, ditrimethylolpropane (isostearate/sebacate), trimethylolpropane trioctanoate, trimethylolpropane triisostearate, diisopropyl adipate, diisobutyl adipate, 2-hexyldecyl adipate, di-2-heptylundecyl adipate, diisostearyl malate, hydrogenated castor oil monoisostearate, N-alkylglycol monoisostearate, octyldodecyl isostearate, isopropyl isostearate, isocetyl isostearate, ethylene glycol di-2-ethylhexanoate, cetyl 2-ethylhexanoate, pentaerythritol tetra-2-ethylhexanoate, octyldodecyl gum ester, ethyl oleate, octyldodecyl oleate, neopentylglycol dicaprate, triethyl citrate, 2-ethylhexyl succinate, dioctyl succinate, isocetyl stearate, diisopropyl sebacate, di-2-ethylhexyl sebacate, diethyl sebacate, dioctyl sebacate, dibutyloctyl sebacate, cetyl palmitate, octyldodecyl palmitate, octyl palmitate, 2-ethylhexyl palmitate, 2-hexyldecyl palmitate, 2-heptylundecyl palmitate, cholesteryl 12-hydroxystearate, dipentaerythritol fatty acid ester, 2-hexyldecyl myristate, ethyl laurate, 2-octyldodecyl N-lauroyl-L-glutamate, di(cholesteryl/behenyl/octyldodecyl)

N-lauroyl-L-glutamate, di(cholesteryl/octyldodecyl) N-lauroyl-L-glutamate,

di(phytosteryl/behenyl/octyldodecyl) N-lauroyl-L-glutamate, di(phytosteryl/octyldodecyl) N-lauroyl-L-glutamate, isopropyl N-lauroylsarcosinate, diisostearyl malate, neopentylglycol dioctanoate, isodecyl neopentanoate, isotridecyl neopentanoate, isostearyl neopentanoate, isononyl isononanoate, isotridecyl isononanoate, octyl isononanoate, isotridecyl isononanoate, diethylpentanediol dineopentanoate, methylpentanediol dineopentanoate, octyldodecyl neodecanoate, 2-butyl-2-ethyl-1 ,3-propanediol dioctanoate, pentaerythrityl tetraoctanoate, pentaerythrityl hydrogenated rosin, pentaerythrityl triethylhexanoate, dipentaerythrityl

(hydroxystearate/stearate/rosinate), polyglyceryl tetraisostearate, polyglyceryl-10

nonaisostearate, polyglyceryl-8 deca(erucate/isostearate/ricinoleate), (hexyldecanoic acid/sebacic acid) diglyceryl oligoester, glycol distearate (ethylene glycol distearate), diisopropyl dimer dilinoleate, diisostearyl dimer dilinoleate, di(isostearyl/phytosteryl) dimer dilinoleate, (phytosteryl/behenyl) dimer dilinoleate, (phytosteryl/isostearyl/cetyl/stearyl/behenyl) dimer dilinoleate, dimer dilinoleyl dimer dilinoleate, dimer dilinoleyl diisostearate, dimer dilinoleyl hydrogenated rosin condensate, dimer dilinoleic acid hardened castor oil,

hydroxyalkyl dimer dilinoleyl ether, glyceryl triisooctanoate, glyceryl triisostearate, glyceryl trimyristate, glyceryl triisopalmitate, glyceryl trioctanoate, glyceryl trioleate, glyceryl

diisostearate, glyceryl tri(caprylate/caprate), glyceryl tri(caprylate/caprate/myristate/stearate), hydrogenated rosin triglyceride (hydrogenated ester gum), rosin triglyceride (ester gum), glyceryl behenate eicosane dioate, glyceryl di-2-heptylundecanoate, diglyceryl myristate isostearate, cholesteryl acetate, cholesteryl nonanoate, cholesteryl stearate, cholesteryl isostearate, cholesteryl oleate, cholesteryl 12-hydroxystearate, cholesteryl ester of macadamia nut oil fatty acid, phytosteryl ester of macadamia nut oil fatty acid, phytosteryl isostearate, cholesteryl ester of soft lanolin fatty acid, cholesteryl ester of hard lanolin fatty acid, cholesteryl ester of long-chain branched fatty acid, cholesteryl ester of long-chain a-hydroxy fatty acid, octyldodecyl ricinoleate, octyldodecyl ester of lanolin fatty acid, octyldodecyl erucate, isostearic acid hardened castor oil, ethyl ester of avocado fatty acid, isopropyl ester of lanolin fatty acid, and the like. Lanolin and lanolin derivatives can also be used as the ester oil provided that they have an oil form.

[0083] Examples of higher fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, undecylenic acid, oleic acid, linolic acid, linolenic acid, arachidonic acid, eicosapentaenoic acid (EPA), docosahexaenoic acid (DHA), isostearic acid, 12-hydroxystearic acid, and the like.

[0084] The fluorinated oil is not particularly limited provided that it is an oil that contains fluorine atoms, and examples thereof include perfluoropolyether, perfluorodecalin,

perfluorooctane, and the like. Perfluoropolyether is preferable from the perspective of chemical stability. Examples of the perfluoropolyether include those having the structural formula: A-(C₃F₆0)_x(CF₂0)_y(C₂F₄0)_z-B (wherein, terminal group A is a -F, -CF₃, -C₂F₅, -C₃F₇, -CF(CF₃)OCF₃, -OF, -OCF₃, -OC₂F₅, -OC₃F₇, or -OCF(CF₃)OCF₃ group; terminal group B is a -CF₃, -C₂F₅, -C₃F₇, or -CF(CF₃)OCF₃ group; and x, y, and z are 0 or positive integers such that x+y+z>1 and are numbers such that a viscosity at 25°C is from 50 to 500,000 cs). Specific examples of the perfluoropolyether include CF₃0-(CF₂CF(CF₃)0)_x(CF₂0)_y-CF₃ (wherein x and y are as described above), CF₃0-(CF₂0)_y(C₂F₄0)_z-CF₃ (wherein y and z are as described above), CF₃0-(CF₂CF(CF₃)0)_x-CF₃ (wherein x is as described above), F-(CF₂CF₂CF₂0)x-C₂F₅ (wherein x is as described above), and the like.

[0085] From the perspectives of lubricity and handling/workability of the film formed from the composition for forming a film of the present invention, the oil included in the oil-containing microparticles (B) preferably accounts for 20 to 90 wt.% (mass%), more preferably accounts for 40 to 90 wt.% (mass%), and even more preferably accounts for 60 to 90 wt.% (mass%), based on the total weight (mass) of the oil-containing microparticles (B). On the other hand, in cases when based on the total weight (mass) of a solid content of the composition for forming a film of the present invention, the content of the oil is preferably from 1 to 50 wt.% (mass%), more preferably from 1 to 45 wt.% (mass%), and even more preferably from 1 to 40 wt.% (mass%) of the solid content.

[0086] The oil-containing microparticles (B) can be manufactured using a conventionally known manufacturing method such as a phase separation method (coacervation method), a liquid drying method, a fusion distribution cooling method, an interracial polymerization method, an in situ polymerization method, a liquid curing and coating method, and the like. Technically, an in situ polymerization method is preferable and, for example, the method described in Japanese Unexamined Patent Application Publication No. H02-1798 can be used.

Specifically, when using a melamine resin as the material for the capsule wall, the

microcapsules can be obtained by reacting melamine and formaldehyde by heating (at 50 to 80°C) in an alkaline aqueous solution (pH from 8 to 10) to obtain a (mono to hexa) methylol melamine prepolymer aqueous solution; and then adding this solution to a slightly acidic O/W emulsion and stirring while heating in a slightly acidic range (pH from 3 to 6), which results in polymers being deposited on the O/W interface.

[0087] A compounded amount of the oil-containing microparticles (B) in the composition for forming a film of the present invention is preferably from 1 to 100 parts by weight (mass), more preferably from 5 to 80 parts by weight (mass), and even more preferably from 10 to 70 parts by weight (mass) per 100 parts by weight (mass) of the activation energy beam curing resin (A).

[0088] The composition for forming a film of the present invention preferably comprises an activation energy beam polymerization initiator (C). Examples of the activation energy beam polymerization initiator (C) include arylketone photoinitiators (e.g. acetophenones,

benzophenones, alkylaminophenones, hydroxyalkylphenones, alkylaminobenzophenones, benzyls, benzoins, benzoin ethers, benzyldimethylketals, benzoylbenzoates,

a-acyloximeesters, and the like), sulfur-containing photoinitiators (e.g. sulfides, thioxanthones, and the like), and acylphosphineoxides (e.g. acyldiarylphosphine oxides and the like). A single activation energy beam polymerization initiator (C) may be used or a combination of two or more types may be used. Additionally, amines or similar photosensitizers may be used in combination with the activation energy beam polymerization initiator (C).

[0089] Specific examples of the activation energy beam polymerization initiator (C) include

4-phenoxydichloroacetophenone, 4-tert-butyl-dichloroacetophenone,

4-tert-butyl-trichloroacetophenone, diethoxyacetophenone,

2-hydroxy-2-methyl-1 -phenylpropane-1 -one,

1 -(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1 -one,

1 -(4-dodecylphenyl)-2-methylpropane-1 -one,

1-{4-(2-hydroxyethoxy)phenyl}-2-hydroxy-2-methyl-propane-1-one,

1 - hydroxycyclohexylphenylketone,

2- methyl-1-{4-(methylthio)phenyl}-2-morpholinopropane-1-one; benzil, benzoin, benzoin methylether, benzoin ethylether, benzoin isopropylether, benzoin isobutylether, benzyl dimethylketal, benzophenone, benzoyl benzoate, methyl benzoyl benzoate,

4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone,

3, 3'-dimethyl-4-methoxy benzophenone,

3,3',4,4'-tetrakis(tert-butylperoxycarbonyl)benzophenone, 9,10-phenanthrenequinone, camphorquinone, dibenzosuberone, 2-ethylanthoraquinone, 4',4"-diethyl isophthalophenone, 1 -phenyl-1 ,2-propanedione-2-(o-ethoxycarbonyl)oxime, a-acyloxime ester,

methylphenylglyoxylate; 4-benzoyl-4'-methyldiphenylsulfide, thioxanthone,

2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone,

2,4,6-trimethylbenzoyldiphenylphosphine oxide, benzoyldiphenylphosphine oxide,

2,6-dimethylbenzoyldiphenylphosphine oxide,

bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, and the like, but the activation energy beam polymerization initiator (C) is not limited thereto.

[0090] A compounded amount of the activation energy beam polymerization initiator (C) in the composition for forming a film of the present invention is preferably from 0.1 to 10 parts by weight (mass) and more preferably from 0.2 to 5 parts by weight (mass) per 100 parts by weight (mass) of the activation energy beam curing resin (A). It is preferable that the amount of the activation energy beam polymerization initiator (C) is within this range because curability will be sufficient, and all of the activation energy beam polymerization initiator (C) will decompose when curing.

[0091] The composition for forming a film of the present invention can comprise at least one type of inorganic microparticles and/or organic microparticles (D). In order to further reduce the coefficient of friction of the film formed from the composition for forming a film of the present invention, the inorganic microparticles and/or organic microparticles (D) are preferably a solid at room temperature. The solid inorganic microparticles and/or organic microparticles (D) can function as a solid lubricant. A single type of the inorganic microparticles or organic microparticles, respectively, can be used, or combinations of two or more types may be used. Moreover, the inorganic microparticles and the organic microparticles may be used together.

[0092] Examples of the inorganic microparticles include sulfides, graphites, boron nitrides, metallic oxides, and similar microparticles. More specific examples include molybdenum disulfide, tungsten disulfide, graphite, hexagonal boron nitride, aluminum oxide, zinc oxide, and similar microparticles.

[0093] Examples of the organic microparticles include fluoro resins, polyolefins, polyamides, and similar microparticles. More specific examples include polytetrafluoroethylene, a tetrafluoroethylene-perfluoroalkylvinylether copolymer, a

tetrafluoroethylene-hexafluoropropylene copolymer, a tetrafluoroethylene-ethylene copolymer, polyvinylidene fluorides, polychlorotrifluoroethylene, polyethylenes, polyamides, and similar microparticles. [0094] A median diameter (measurement using a laser diffraction/scattering type particle size distribution) of the inorganic microparticles or organic microparticles is, in general, preferably from 0.1 to 50 μηη, more preferably from 1 to 30 Mm, and even more preferably from 1 to 20 μιη.

[0095] A compounded amount of the inorganic microparticles and/or organic microparticles (D) in the composition for forming a film of the present invention is not particularly limited but is preferably from 1 to 100 parts by weight (mass) and more preferably from 10 to 80 parts by weight (mass) per 100 parts by weight (mass) of the activation energy beam curing resin (A). If the amount of the inorganic microparticles and/or organic microparticles (D) is within this range, effects of reducing the coefficient of friction of the film can be obtained and the strength of the film can be maintained.

[0096] The composition for forming a film of the present invention can further comprise at least one type of a solvent (E). The solvent (E) can enhance the applicability and bonding to a substrate of the composition for forming a film of the present invention. A single type of solvent may be used or a combination of two or more types may be used.

[0097] Preferable examples of the solvent (E) include water or, alternately, organic solvents such as ethyl alcohol, butyl alcohol, isopropyl alcohol, and similar lower alcohols; methyl isobutyl ketone, methyl ethyl ketone, acetone, and similar ketones; dioxane, diethyleneglycol dimethylether, tetrahydrofuran, methyl-t-butyl ether, and similar ethers; methyl cellosolve, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether acetate, and similar

cellosolves; and the like. In addition, methyl acetate, ethyl acetate, butyl acetate, pentyl acetate, ethyl lactate, diethyl succinate, diethyl adipate, dibutyl phthalate, dioctyi phthalate, and similar esters such as dibasic acid esters and the like; chlorinated and fluorinated hydrocarbons, trichloroethane, and similar halogenated hydrocarbons such as chlorinated hydrocarbons, fluorinated hydrocarbons and the like; toluene, xylene, hexane, and similar hydrocarbons; and the like can be used. Preferably, a suitable solvent for forming the film is selected depending on the type of substrate, but from the perspective of workability, water or a lower alcohol is preferable.

[0098] A compounded amount of the solvent (E) in the composition for forming a film of the present invention is not particularly limited but is preferably from 1 to 500 parts by weight (mass) and more preferably from 50 to 300 parts by weight (mass) per 100 parts by weight (mass) of the activation energy beam curing resin (A).

[0099] As necessary, the composition for forming a film of the present invention may comprise one or more types of additives such as a UV absorber, a photostabilizer, an antioxidant, a thermal polymerization inhibitor, a leveling agent, an anti-foaming agent, a ' thickening agent, an anti-settling additive, a pigment (an organic coloration pigment or

inorganic pigment), a coloration dye, an infrared radiation absorber, an optical brightener, a dispersing agent, conductive microparticles, an antistatic agent, an antifogging agent, a coupling agent, and the like.

[0100] Preferable examples of the UV absorber include those commonly used as UV absorbers for synthetic resins such as benzotriazole-based UV absorbers,

benzophenone-based UV absorbers, salicylic acid-based UV absorbers, phenyltriazine-based UV absorbers, and the like. Specific examples thereof include the compound described in paragraph 0078 of Japanese Unexamined Patent Application Publication No. H11-268196. Because the coating-use composition of the present invention comprises the polymerizable polyfunctional compound (a-1), a UV absorber having a photopolymerizable functional group in the molecule such as 2-{2-hydroxy-5-(2-acryloyloxyethyl)phenyl}benzotriazole,

2-hydroxy-3-methacryloyloxypropyl-3-(3-benzotriazole-4-hydroxy-5-tert-butylphenyl)propionate, or the like is particularly preferable.

[0101] The photostabilizer is preferably a hindered amine-based photostabilizer that is commonly used as a photostabilizer for synthetic resins. Specific examples thereof include the compound described in paragraph 0080 of Japanese Unexamined Patent Application Publication No. H11-268196. In the present invention, a photostabilizer having a polymerizable functional group in the molecule such as

N-methyl-4-methacryloyloxy-2,2,6,6-tetramethylpiperidine, and the like is particularly preferable.

[0 02] The antioxidant is preferably a hindered phenol-based antioxidant such as

2,6-di-tert-butyl-p-cresol, and the like; a phosphorous-based antioxidant such as triphenyl phosphite and the like; or the like. Examples of the thermal polymerization inhibitor include hydroquinone monomethyl ether and the like. Examples of the leveling agent include silicone-based leveling agents, acrylic resin-based leveling agents, and the like.

[0103] Examples of the anti-foaming agent include silicone-based anti-foaming agents such as polydimethyl siloxane, and the like. Examples of the thickening agent include polymethyl methacrylate-based polymers, hydrogenated castor oil-based compounds, fatty acid amide-based compounds, and the like.

[0104] Examples of the organic coloration pigment include condensed polycyclic-based organic pigments, phthalocyanine-based organic pigments, and the like. Examples of the inorganic pigment include titanium dioxide, cobalt oxide, molybdenum red, titanium black, and the like. Examples of the coloration dye include organic solvent soluble azo-based metal complex salt dyes, organic solvent soluble phthalocyanine-based dyes, and the like.

[0105] Examples of the infrared radiation absorber include polymethine-based,

phthalocyanine-based, metal complex-based, aminium-based, diimmonium-based,

anthoraquinone-based, dithiol metal complex-based, naphthoquinone-based,

indophenol-based, azo-based, triarylmethane-based compounds, and the like.

[0 06] Examples of the conductive microparticles include zinc, aluminum, nickel, and similar metal powders, iron phosphide, antimony-doped tin oxide, and the like.

[0107] Examples of the antistatic agent include nonionic antistatic agents, cationic antistatic agents, anionic antistatic agents, and the like. [0108] Examples of the coupling agent include silane coupling agents, titanate coupling agents, and the like.

[0109] The composition for forming a film of the present invention can be prepared by, for example, mixing components (A) and (B), and also, as necessary components (C) and/or (D) and/or (E) and, furthermore, any other optional components such as the additives described above or the like.

[0 10] A film can be formed by applying the composition for forming a film of the present invention to a substrate surface and, thereafter, curing the composition by irradiation with activation energy beams. The present invention also relates to a substrate comprising a surface on which such a film is formed. In cases where the solvent (E) is included, the composition for forming a film of the present invention is preferably cured by irradiation with activation energy beams after drying.

[0111] The application of the composition for forming a film of the present invention to the substrate surface can be carried out using any technique. Examples of application techniques that can be used include dipping methods, spincoat methods, flowcoat methods, spraying methods, bar-coating methods, gravure coating methods, roll coating methods, blade coating methods, air knife coating methods, and the like. A thickness of the film formed on the substrate surface is not particularly limited, but the thickness is preferably from 1 to 50 μηη and more preferably from 5 to 30 pm.

[0112] One type of activation energy beams may be used or two or more types may be used. Examples of activation energy beam sources that can be used include xenon lamps, low-pressure mercury lamps, high-pressure mercury lamps, ultra high-pressure mercury lamps, metal halide lamps, carbon arc lamps, tungsten lamps, and similar ultraviolet light irradiation devices, electron irradiation devices, X-ray radiation devices, high frequency generation devices, and the like.

[0113] Irradiation time of the activation energy beams can be appropriately changed according to the type of each component in the composition for forming a film of the present invention, the thickness of the film, the activation energy beam source, and other conditions but, in general, irradiation from one second to one hour is sufficient. Furthermore, for the purpose of completing the curing reaction, heat treating may be performed after the irradiation with the activation energy beams. For examples, the heating can be performed in a temperature range from 100 to 300°C, but is preferably performed in a temperature range from 120 to 250°C, and more preferably in a temperature range from 130 to 200°C.

[0114] The thickness of the cured film is not particularly limited but is preferably from 0.1 to

30 μηι and more preferably from 0.5 to 20 μιη.

[0115] The cured film has superior sliding durability, excellent bonding with a substrate, and superior followability with regards to a deformation in cases when the substrate deforms.

[0116] In the present invention, the surface coated substrate can be manufactured via a step of applying the composition for forming a film described above to a substrate surface, and then irradiating the substrate surface with activation energy beams, but it is not necessary to heat the substrate. Therefore, a film having the superior characteristics described above can be formed on any type of substrate.

[0117] Therefore, the substrate may be fabricated from any type of material, either inorganic or organic. Examples of inorganic substrates include substrates formed from soda lime glass, quartz glass, heat resistant glass, or a similar transparent or semi-transparent glass or indium tin oxide (ITO) or a similar metallic oxide; and substrates formed from silicon, aluminum, iron, or a similar metal. Examples of organic substrates include substrates formed from plastic or rubber. Examples of the substrates formed from plastic or rubber include substrates formed from polycarbonate, polymethyl methacrylate resin, polymethacrylic imide resin, polystyrene resin, polyvinyl chloride resin, unsaturated polyester resin, polyolefin resin, ABS resin, MS (methyl methacrylate-styrene) resin, and the like. INDUSTRIAL APPLICABILITY

[0118] The composition for forming a film and the method for forming a film of the present invention can be suitably used on various substrates for which superior slidability is required. Examples thereof include uses as surface coatings on crank shafts, slide bearings, pistons, gaskets, gears, door panels, instrument panels, door locks, timing belts; body seals, glass runs, and weather stripping for a sunroof; and the like.

EXAMPLES

[0119] Hereinafter, the present invention will be described in detail based on Practical Examples and Comparative Examples. However, the present invention is not limited to these Practical Examples. Note that terms in the Tables are as defined below and numbers in the Tables are expressed in terms of parts by weight (mass).

[0120] Photocurable urethane acrylate A:

Film forming aqueous polycarbonate-based polyurethane resin emulsion: Reaction product of polycarbonate diol, polyisocyanate, and a compound having hydroxyl groups and

(meth)acryloyl groups (solid content: 30%, viscosity: 20 mPas)

[0121] Photocurable urethane acrylate B:

Film forming aqueous polyester-based polyurethane resin emulsion: Reaction product of polyester polyol, polyisocyanate, and a compound having hydroxyl groups and (meth)acryloyl groups (solid content: 32%, viscosity: 50 mPas)

[0122] Photocurable epoxy acrylate:

Film forming epoxy acrylate resin (solid content: 100%, viscosity: 8,000 mPas)

[0123] Epoxy resin:

Liquid epoxy resin (jER828, manufactured by Mitsubishi Chemical Corporation; viscosity:

120,000 to 150,000 mPas, epoxy equivalent weight: 184 to 194)

[0124] Radical photoinitiator A:

a-aminoalkylphenone-based photoinitiator (IRGACURE907, manufactured by BASF Japan Ltd. ; solid content: 100%)

[0125] Radical photoinitiator B:

a-hydroxyalkylphenone-based photoinitiator (DAROCUR1 173, manufactured by BASF Japan Ltd.; solid content: 100%)

[0126] Amine-based curing agent:

jERCure ST14, manufactured by Mitsubishi Chemical Corporation (amine value: 415 to 455, viscosity: 1 ,000 to 4,000 mPas (at 50°C), solid content: 100%)

[0127] Polvtetrafluoroethylene powder:

Polytetrafluoroethylene resin powder having a median diameter measured using a laser diffraction/scattering type particle size distribution of 2 to 4 m.

[0128] Aluminum oxide powder:

Aluminum oxide powder having a median diameter measured using a laser

diffraction/scattering type particle size distribution of 1 pm.

[0129] Molybdenum disulfide:

Molybdenum disulfide microparticles having a median diameter measured using a laser diffraction/scattering type particle size distribution of 3 to 6 μητι.

[0130] Graphite:

Squamous graphite having a median diameter measured using a laser diffraction/scattering type particle size distribution of 3 to 5 μηη.

[0131 ] Preparation of fluorinated oil-containing microcapsules

An emulsion was obtained by adding 200 ml of perfluoropolyether oil having a kinetic viscosity of 250 mm²/s to 200 g of a 5% aqueous solution of ethylene-maleic anhydride copolymer (EMI-31 , manufactured by Monsanto Chemical Company) adjusted to a pH of 4.5, and then emulsifying/dispersing using a homomixer. 100 g of a methylol-melamine resin aqueous solution (Sumirez Resin 613, manufactured by Sumitomo Chemical Co. , Ltd.) having a solid content adjusted to 17 wt.% was added to this emulsion, the temperature of the system was raised to 55°C, and the system was stirred for about one hour. Thereafter, the pH was adjusted to 5.5 and the system was further stirred for two hours and then gradually cooled to room temperature. Next, the pH was lowered to 3.5 using 10% hydrochloric acid, and then 160 g of a 25% methylol-melamine resin aqueous solution was added to the system. Then the temperature was raised to 50°C and the system was stirred. Thereafter, the pH was adjusted to 3.7, the temperature was raised to 60°C, and the system was further mixed for two hours while adjusting the mixing speed. About 200 ml of water was added and the system was cooled to room temperature. Thereby a microcapsule dispersion was obtained. The obtained microcapsule dispersion was dewatered and dried at room temperature for 24 hours. Thereby, fluorinated oil-containing microcapsules were obtained. The median diameter of the obtained microcapsules measured using a laser diffraction/scattering type particle size distribution was about 10 pm. Moreover, 80 wt.% of the obtained microcapsules was the perfluoropolyether oil.

[0132] Practical Examples 1 to 8 and Comparative Examples 1 to 3

The resins (binders) and the solvents shown in Tables 1 to 3 were agitated and mixed at the compounding ratios shown in Tables 1 to 3, and then the photoinitiators shown in Tables 1 to 3 were added at the compounding ratios shown in Tables 1 to 3 and dissolved therein for each of Practical Examples 1 to 8 and Comparative Examples 1 and 2. Thereafter, the fluorinated oil-containing microcapsules and/or the solid lubricants shown in Tables 1 to 3 were added at the compounding ratios shown in Tables 1 to 3, and the mixtures were agitated and mixed. Thereby coating compositions were obtained.

[0133] The resins and the solvents shown in Table 3 were agitated and mixed at the compounding ratios shown in Table 3, and then the curing agent shown in Table 3 was added at the compounding ratio shown in Table 3 and dissolved therein for Comparative Example 3. Thereafter, the fluorinated oil-containing microcapsules shown in Table 3 were added at the compounding ratio shown in Table 3, and the mixture was agitated and mixed. Thereby a coating composition was obtained. [0134] Table 1

Practical Practical Practical Practical

Composition Example Example Example Example

5 6 7 8

Photocurable

100 - - - urethane acrylate B

Resin

Photocurable epoxy

- 100 100 100 acrylate

Radical photoinitiator

2 - - - A

Photoinitiator

Radical photoinitiator

- 2 2 2 B

Fluorinated

Microcapsules oil-containing 15 60 15 15 microcapsules

Molybdenum disulfide - - 10 -

Solid lubricant

Graphite - - - 10

Ion exchange water 240 - - -

Solvent

Isopropyl alcohol - 75 75 75

Microcapsules/resin weight (mass)

0.15 0.60 0.15 0.15 ratio

Solid lubricant/resin weight (mass)

- - 0.10 0.10 ratio [0136] Table 3

[0137] Cured film forming

The coating compositions of Practical Examples 1 to 8 and Comparative Examples 1 to 3 were respectively spray coated on surfaces of samples formed from each of the substrates shown in Tables 4 to 6, so as to form a film having a thickness of 10 to 15 Mm. Next, after allowing the samples to sit at 25°C for 10 minutes so as to volatilize the solvent, UV light at a cumulative luminous energy of 1 ,000 to 1 ,500 mJ/cm² was irradiated using a 250 W handy type UV irradiator (manufactured by ASUMI GIKEN, Limited). Thereby, cured films were formed.

[0138] The coating composition of Comparative Example 3 was spray coated on the substrate surface shown in Table 6 so as to form a film having a thickness of 10 to 15 prn. Then, the substrate was allowed to sit at 25°C for 10 minutes in order to volatilize the solvent. Thereafter, the substrate was heated at 130°C for 30 minutes. Thereby, a cured film was formed.

[0139] Note that terms in the Tables are as defined below.

[0140] PC resin board:

lupilon S-3000, manufactured by Mitsubishi Engineering-Plastics Corporation

[0141] ABS resin board:

Toughace R, manufactured by Sumitomo Bakelite Co., Ltd. [0142] EPDM rubber board:

Ethylene propylene diene monomer crosslinked product, manufactured by Kanda Gomu Kagaku Corporation

[0143] SPCC steel plate:

SPCC-SB, manufactured by Nisshin Steel Co., Ltd.

[0144] Next, the coefficient of friction of each sample on which the cured film was formed was measured, and durability and followability were evaluated as described below. The coefficient of friction measurement results and the durability and followability evaluation results are shown in Tables 4 to 6. Note that the "-" symbol in Table 5 indicates a case where the coefficient of friction was not measured.

[0145] Coefficient of friction

Using a reciprocating dynamic friction abrasion tester on the samples on which the cured film was formed, the kinetic coefficient of friction (unit: μ) of the sample surfaces after sliding 100,000 times against a 1/2 inch steel sphere was recorded under the following conditions: Sliding speed= 7 mm/s; Load= 1.5 kG; Sliding distance (stroke)= 2 mm. In cases where the film peeled from the sample surface and the coefficient of friction increased partway through the testing, the kinetic coefficient of friction (unit: μ) at the time of peeling was recorded.

[0146] Durability

The number of cycles at the completion of the coefficient of friction testing was recorded. In cases where the film peeled from the sample surface and the coefficient of friction increased partway through the coefficient of friction testing, the number of cycles at the time of peeling was recorded.

[0147] Followability

Using an AGS Series Shimadzu Autograph (manufactured by Shimadzu Corporation), the EPDM rubber board (thickness: 1 mm) on which the cured film was formed was stretched to an elongation of 250% at a rate of pulling of 50 mm/min and, thereafter, was allowed to sit at 25°C for three days. Then, the board was released from the tensed state and the presence or absence of peeling of the coated surface was confirmed using a microscope. The degree of peeling was evaluated according to the following standards.

·: No cracking or peeling observed

o: Very minor cracking but no peeling observed

Δ: Cracking and very minor peeling observed

x: Cracking and peeling observed

[0148] Table 4

[0149] Table 5

[0150] Table 6

[0151] From Tables 4 to 6, it is clear that the films of the Practical Examples have excellent sliding characteristics and followability. On the other hand, with the films obtained via Comparative Examples 1 and 2, in which the fluorinated oil-containing microcapsules were not used, the coefficient of friction increased and sliding durability decreased greatly. Moreover, with the film obtained via Comparative Example 3, in which the photocurable resin was not used, the coefficient of friction increased, sliding durability decreased, and followability was negatively affected.

Claims

1. A composition for forming a film comprising: (A) an activation energy beam curing resin, and (B) oil-containing microparticles.

2. The composition for forming a film according to claim 1 , wherein the activation energy beams are ultraviolet light.

3. The composition for forming a film according to claim 1 or 2, wherein the activation energy beam curing resin (A) is radical-polymerizable.

4. The composition for forming a film according to any one of claims 1 to 3, further comprising: (C) an activation energy beam polymerization initiator.

5. The composition for forming a film according to claim 4, wherein from 0.1 to 10 parts by weight of the activation energy beam polymerization initiator (C) are comprised per 100 parts by weight of the activation energy beam curing resin (A).

6. The composition for forming a film according to any one of claims 1 to 5, wherein the oil-containing microparticles (B) are microcapsules comprising a capsule wall encapsulating at least one type of oil, optionally wherein the capsule wall comprises at least one type of thermosetting resin..

7. The composition for forming a film according to any one of claims 1 to 6, wherein the oil is a fluorinated oil.

8. The composition for forming a film according to any one of claims 1 to 7, wherein a diameter of the oil-containing microparticles (B) is from 1 to 30 μηι.

9. The composition according to any one of claims 1 to 8, wherein the oil accounts for 20 to 90 wt.% of a total weight of the oil-containing microparticles (B).

10. The composition for forming a film according to any one of claims 1 to 9, wherein from 1 to 100 parts by weight of the oil-containing microparticles (B) are comprised per 100 parts by weight of the activation energy beam curing resin (A).

11. The composition for forming a film according to any one of claims 1 to 10, further comprising: at least one type of (D) inorganic microparticles and/or organic microparticles.

12. The composition for forming a film according to any one of claims 1 to 1 1 , further comprising: at least one type of (E) solvent.

13. A method for forming a film comprising: applying the composition for forming a film described in any one of claims 1 to 12 to a substrate surface, and then irradiating the substrate surface with activation energy beams.

14. A substrate comprising a surface on which a film is formed via the method for forming a film described in claim 13.

15. A method for manufacturing a surface coated substrate comprising a step of applying the composition for forming a film described in any one of claims 1 to 12 to a substrate surface, and then irradiating the substrate surface with activation energy beams.