WO2008035621A1

WO2008035621A1 - Curable composition

Info

Publication number: WO2008035621A1
Application number: PCT/JP2007/067890
Authority: WO
Inventors: Kazuhiko Ueda; Kazuhide Fujimoto; Takeshi Sonoda
Original assignee: Kaneka Corporation
Priority date: 2006-09-22
Filing date: 2007-09-13
Publication date: 2008-03-27
Also published as: JPWO2008035621A1; JP5297807B2

Abstract

Disclosed is a curable composition which can provide a cured product having good weather resistance without impairing the properties of the cured product. The curable composition comprises: (A) an organic polymer having at least one alkenyl group in the molecule; (B) a compound having at least one hydrosilyl group in the molecule; (C) a hydrosilylating catalyst; and (D) a compound having a cyclic skeleton composed of N atoms and C atoms in the molecule and also having a univalent organic group on at least one N atom, wherein the atom directly bound to the N atom is a C atom.

Description

Specification

Curable composition

Technical field

[0001] The present invention relates to a curable composition. More specifically, a curable composition comprising an organic polymer having an alkenyl group in one molecule, a compound having at least one hydrosilyl group in one molecule, a hydrosilylation catalyst, and a specific hindered amine compound as essential components. Related to things.

Background art

[0002] A curable composition in which a polyoxypropylene-based polymer having an alkenyl group and a compound having a hydrosilyl group are reacted in the presence of a platinum catalyst is a fast-curing property, a deep-curing property, and various adherends having this structure. In consideration of properties such as affinity to water, hydrophilicity, and chemical stability, various applications such as moldings and adhesives are being studied. As such a curable compound, for example, a curable composition is proposed in which a polyoxypropylene polymer having an alkenyl group and an organohydropolyene polysiloxane having silicon-bonded hydrogen in one molecule are reacted in the presence of a platinum catalyst. (For example, refer to Patent Document 1). As a method for improving the compatibility and mechanical properties of the curable composition, a method using an organohydrodiene polysiloxane having a phenyl group in the side chain as a compound having a hydrosilyl group has been proposed. (For example, see Patent Document 2). In addition, an adhesive composition comprising a polyoxypropylene polymer having an alkenyl group, a compound having a hydrosilyl group, and a hydrosilylation catalyst has been proposed (see, for example, Patent Documents 3 and 4). However, these curable compositions were not always good in terms of weather resistance.

Patent Document 1: Japanese Patent Application Laid-Open No. 60-55056

Patent Document 2: JP-A-7-300555

Patent Document 3: Japanese Patent Laid-Open No. 4145188

Patent Document 4: WO2005 / 033239

Disclosure of the invention

Problems to be solved by the invention [0003] An object of the present invention is to provide a curable composition having good weather resistance. Means for solving the problem

As a result of various studies, the present inventors have found that a cured product that exhibits good weather resistance without impairing the properties of the cured product can be obtained, and the present invention has been completed. That is, the above-described problems can be achieved by the following novel curable composition.

[0005] 1) an organic polymer (A) having at least one alkenyl group in one molecule;

Compound (B) having at least one hydrosilyl group in one molecule,

Hydrosilylation catalyst (C), a compound having a cyclic skeleton composed of N atoms and C atoms in the molecule, wherein the atom directly connected to the N atom is C on at least one N atom. The curable composition containing the compound (D) in which the organic group of exists.

[0006] 2) The curable composition according to 1), wherein the compound (D) is a compound in which one N atom is present in the cyclic skeleton and / or a compound in which two N atoms are present in the cyclic skeleton. object

3) The compound (D) is a 5-membered ring and / or a 6-membered ring having one N atom, 1

) The curable composition as described.

[0007] 4) The compound (D) is a 5-membered ring and / or a 6-membered ring having 2 N atoms, 1

) The curable composition as described.

[0008] 5) The curing according to any one of 1) to 4), wherein the compound (D) has an alkyl group having 1 to 18 carbon atoms on at least one carbon atom constituting the cyclic skeleton. Sex composition.

[0009] 6) The compound (D) is a compound represented by the following general formula (1):

[0010] [Chemical 1]

[Wherein X is an organic group in which the atom bonded to N is C, and R ¹ , R ¹ R, and R ¹⁴ have 1 to 8 carbon atoms. Each of which may be the same or different. The curable composition according to claim 1, wherein the content is 0.0;! To 20 parts by weight with respect to 100 parts by weight of the organic polymer (A). object.

[0012] 7) The curable composition according to 1) to 6), wherein the main chain of the organic polymer (A) is essentially polyoxyalkylene or poly (meth) acrylate. .

[0013] 8) The curable composition according to 7), wherein the main chain of the organic polymer (A) is essentially polyoxypropylene.

[0014] 9) The curable composition according to any one of 6) to 8), wherein X in the general formula (1) is an acyl group.

[0015] 10) The curable composition according to any one of 1) to 9), wherein the hydrosilylation catalyst (C) is chloroplatinic acid and / or platinum bursiloxane.

11) is the metal content force of the hydrosilylation catalyst (C) S, wherein the organic polymer ^{(A) 6 X 10- 4 ~3} X 10- 3 parts by weight per 100 parts by weight, curing according to 10) Sex composition.

[0016] 12) The content of the compound (D) is 0.0 with respect to 100 parts by weight of the organic polymer (A).

The curable composition according to 1) to 5), which is! To 20 parts by weight.

The invention's effect

[0017] The curable composition of the present invention is a curable composition comprising an organic polymer having an alkenyl group and a compound having a hydrosilyl group as essential components, and an organic compound having a specific structure. By adding, the weather resistance remarkably excellent is expressed.

BEST MODE FOR CARRYING OUT THE INVENTION

[0018] As the organic polymer (A) having at least one alkenyl group in one molecule of the present invention, various types without particular limitation can be used, and polyoxyalkylenes such as polyoxypropylene polymers can be used. Examples thereof include polyalkylene-based polymers such as polymer-based polymers and polyisobutylene-based polymers, and poly (meth) acrylates. As the organic polymer having at least one alkenyl group in one molecule, a single type of organic polymer may be used, or a plurality of types of organic polymers may be mixed and used. When using a mixture of two or more types, these organic polymers are compatible with each other!

As the polyoxyalkylene polymer, specifically, the main chain of the polymer has the general formula (2 And those having a repeating unit represented by General formula (2):

-R'-O- (2)

(Wherein R ¹ is a divalent alkylene group)

R ¹ in the general formula (2) is preferably a linear or branched alkylene group having 1 to 14, more preferably 2 or more carbon atoms. Specific examples of the repeating unit represented by the general formula (2) include CH 2 O, —CH 2 CH 2 O, —CH 2 CH (CH 2) 0 1, CH 2 CH 3 (CH 2) 0 1, —CH 2 C 3 (CH 2) 2 O 2 CH 2 CH 2 CH 2 O 3 and the like can be mentioned. The main chain skeleton of the polyoxyalkylene polymer may be composed of only one type of repeating unit, or may be composed of two or more types of repeating units. In particular, from the viewpoint of availability and workability, a polymer having —CH 2 CH 2 (CH 3) 0 — as the main repeating unit is preferred. In addition, the main chain of the polymer may contain a repeating unit other than the oxyalkylene group. In this case, the total of the oxyalkylene units in the polymer is preferably 80% by weight or more, particularly 90% by weight or more.

[0020] The molecular weight of the organic polymer (A) of the present invention is preferably from 1,000 to 10,000 in terms of number average molecular weight; more preferably from 6,000 to 70,000 and more preferably from 10,000 to 000 50,000 are particularly preferred. When the number average molecular weight is less than 1,000, the obtained cured product tends to be too brittle, and good physical properties of the cured product cannot be obtained. On the other hand, if the number average molecular weight exceeds 100,000, the viscosity becomes too high and the workability is remarkably deteriorated. The number average molecular weight can be measured by various methods, but can be easily measured by gel permeation chromatography (GPC).

[0021] The structure of the organic polymer (A) of the present invention may be a linear polymer, a branched polymer, or a mixture thereof.

[0022] The alkenyl group of the organic polymer (A) of the present invention is not particularly limited, but an alkenyl group represented by the following general formula (3) is preferably used. General formula (3):

HC = C (R ² ) — (3)

(Wherein R ² is hydrogen or a methyl group)

There are no particular restrictions on the manner in which the alkenyl group is bonded to the main chain of the organic polymer (A), but examples include a direct bond of an alkenyl group, an ether bond, an ester bond, a carbonate bond, a urethane bond, and a urea bond. It is done. [0023] Specific examples of the organic polymer (A) of the present invention include a compound represented by the general formula (4):

{HC = C (R ³ ) -R ⁴ -0} aR ⁵ (4)

(Wherein R ³ is hydrogen or a methyl group, R ⁴ is a divalent hydrocarbon group having 120 carbon atoms and includes one or more ether groups! /, May! /, R ⁵ is a polyoxyalkylene polymer residue, and a is a positive integer.). Specifically, R ⁴ is capable of mentioning —CH 2 —CH 2 CH 2 —CH 2 CH 2 CH 2 CH 2 (CH 2) 2 CH 2 CH 2 CH 2 CH 2 CH 2 OCH 2 CH 2 CH 2 CH 2 CH 2 CH 3 — or the like. From the viewpoint of easy synthesis, CH— is preferred.

[0024] Other specific examples of the organic polymer (A) of the present invention include a compound represented by the general formula (5):

{HC = C (R ³ ) -R ⁴ -OC (= 0)} aR ⁵ (5)

(Wherein R ³ , R ⁴ , R ⁵ and a are the same as above), and a polymer having an ester bond.

[0025] Further, the following general formula (6):

{HC = C (R ³ )} a R ⁵ (6)

(In the formula, R ³ , R ⁵ and a are the same as above). Furthermore, the following general formula (7):

^{{HC = C (R 3)} -R 4 -OC (= 0) 0} aR 5 (7)

(Wherein R ³ , R ⁴ , R ⁵ and a are the same as above), a polymer having a carbonate bond.

[0026] The method for polymerizing a polyoxyalkylene polymer, which is a preferred embodiment of the organic polymer (A) of the present invention, is usually an oxyalkylene disclosed in JP-A-50-13496. Polymerization method (anion polymerization method using caustic), disclosed in JP-A-50-149797, etc. Polymerization method by chain extension reaction method using this polymer as a raw material, disclosed in JP-A-7-179597 Ponorphyrin / aluminum disclosed in JP-A 61-197631, JP-A 61 215622, JP-A 61-215623, JP-A 61-218632 Polymerization method using complex catalyst, polymerization method using double metal cyanide complex catalyst disclosed in JP-B-46-27250 and JP-B-59-15536, etc., polyphosphine disclosed in JP-A-10-273512, etc. For polymerization methods using zen salt catalysts Get more power.

[0027] Practically, a method using a double metal cyanide complex catalyst is preferable from the viewpoint of availability of the catalyst and polymerization stability. A known method can be used for producing the double metal cyanide complex catalyst.

For example, U.S. Pat.Nos. 3,278,457, 3,278,459, 5,891, 818, 5,767,323, 5,767,323, 5,536,883 No. 5, 482, 908, No. 5, 15 8, 922, No. 4, 472, 560, No. 6, 063, 897, No. 5, 891, 818, No. 5, 627, 122 5, 482, 908, 5, 470, 813, 5, 158, 922 and the like are preferable.

[0028] A method for synthesizing a polyoxyalkylene polymer having at least one alkenyl group in one molecule, which is a preferred embodiment of the organic polymer (A) of the present invention, is a polyoxyalkylene polymer. In addition to the usual polymerization method (cayon polymerization method using caustic alkali) and a chain extension reaction method using this polymer as a raw material, JP-A 61-197631, JP-A 61-215622, It can be obtained by the methods described in JP-A-61-215623, JP-A-61-218632, JP-B-46-27250, JP-B-59-15336, etc.

Yes

[0029] Various methods can be used for introducing an alkenyl group into the polyoxyalkylene polymer. For example, it can be introduced by copolymerization of a monomer having an alkenyl group such as allyl glycidyl ether and an oxyalkylene monomer. In addition, by reacting an oxyalkylene polymer having a functional group such as a hydroxyl group or an alkoxide group in the main chain or side chain with an organic compound having a functional group and an alkenyl group reactive to these functional groups. An alkenyl group can be introduced into the main chain or side chain. In particular, when an alkenyl group is present at the end of the main chain of the polymer, the effective network chain length in the cured product is increased, and it is possible to obtain a cured product having excellent mechanical properties. Les.

[0030] Examples of the organic compound having a functional group and an alkenyl group reactive to the above functional group include acrylic acid, methacrylic acid, butyl acetate, acrylic acid chloride, and acrylic acid bromide. Acids, rides, acid anhydrides of unsaturated fatty acids having 3 to 20 carbon atoms, Aryl Chloroformate, Aryl Chloride, Aryl Bromide, Bulle (Chloromethyl) Benzene, Aryl (Chloromethinore) benzene, Aryl (Promomethinole) benzene, Arinore (Chloromethylenole) Ether, Aryl (Chloromethoxy) benzene, 1-Butyl (Chloromethylenole) ) Ethenore, 1 Hexeninole (chloromethoxy) benzene, arinoleoxy (chloromethinole) benzene, etc.

The poly (meth) acrylate polymer is not particularly limited, but the (meth) acrylic acid ester monomer constituting the main chain of the (meth) acrylic acid ester polymer is not particularly limited. Can be used. For example, (meth) acrylic acid, (meth) methyl acrylate, (meth) ethyl ethyl acrylate, (meth) acrylic acid n-propyl, (meth) acrylic acid isopropyl, (meth) acrylic acid n- Butyl, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) N-heptyl acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, noel (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, ( (Meth) acrylic acid phenyl, (meth) acrylic acid tolyl, (meth) benzyl acrylate, (meth) acrylic acid 2-methoxyethyl, (meth) 3-methoxybutyl crylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylic acid 2-amino Examples include (meth) acrylic monomers such as ethyl, γ- (methacryloyloxypropyl) trimethoxysilane, γ-remethoxysilane, methacryloyloxymethyltriethoxysilane, and methacryloyloxime ethylene oxide adduct. In the acrylic ester polymer composed of the (meth) acrylic ester monomer, the following bull monomers can be copolymerized together with the (meth) acrylic ester monomer. Examples of the butyl monomers include styrene monomers such as styrene, butyltoluene, α-methylstyrene, chlorostyrene, styrene sulfonic acid and salts thereof; and benzene-containing butyl systems such as butyltrimethoxysilane and butyltriethoxysilane. Monomers; maleic anhydride, maleic acid, monoalkyl esters and dialkyl of maleic acid Estenole: fumanoleic acid, monophenolo quinole estenole and diano quinole estenole of fumanoleic acid; maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecyl Maleimide monomers such as maleimide, stearylmaleimide, phenylmaleimide and cyclohexylmaleimide; nitrile group-containing butyl monomers such as acrylonitrile and methacrylonitrile; amide group-containing butyl monomers such as acrylamide and methacrylamide; butyl acetate and propionic acid Bull esters, such as bull, bivalinate, benzoate and cinnamate; alkenes such as ethylene and propylene; conjugates such as butadiene and isoprene; Alkylidene, salts of Ariru, § Lil alcohol. These may be used alone or a plurality of these may be copolymerized. Of these, a polymer composed of a styrene monomer and a (meth) acrylic acid monomer is preferred in view of the physical properties of the product. More preferred is a (meth) acrylic polymer comprising an acrylate monomer and a methacrylic acid ester monomer, and particularly preferred is an acrylic polymer comprising an acrylate monomer. In applications where flexibility of the cured product is required, such as an adhesive, a butyl acrylate monomer is preferred from the standpoint of physical properties such as low modulus and high elongation of the cured product. On the other hand, in applications that require oil resistance such as automobile applications, a copolymer mainly composed of ethyl acrylate is more preferable. This polymer mainly composed of ethyl acrylate is excellent in oil resistance but tends to be slightly inferior in low-temperature characteristics (cold resistance). Therefore, in order to improve the low-temperature characteristics, a part of ethyl acrylate is butyl acrylate. It is also possible to replace it with. However, as the ratio of butyl acrylate is increased, its good oil resistance is impaired, so for applications that require oil resistance, the ratio is preferably 40 mol% or less, and more preferably 30 mol. % Or less is more preferable. It is also preferable to use 2-methoxyethyl acrylate or 2-ethoxyethyl acrylate in which oxygen is introduced into the side chain alkyl group in order to improve the low temperature characteristics without impairing oil resistance. However, since heat resistance tends to be inferior due to the introduction of an alkoxy group having an ether bond in the side chain, the ratio is preferably 40 mol% or less when heat resistance is required. According to various uses and required purposes, it is possible to obtain a suitable polymer by changing the ratio in consideration of required physical properties such as oil resistance, heat resistance, and low temperature characteristics. For example, the limitation is As an example, a high level of oil resistance, heat resistance, and low-temperature properties can provide a good balance of physical properties such as ethyl acrylate / butyl acrylate / 2-methoxyethyl acrylate (molar ratio of 40-50 / 20- 30/30 to 20). In the present invention, these preferable monomers may be copolymerized with other monomers, and further block copolymerized. In this case, these preferable monomers may be contained in a weight ratio of 40% or more. preferable. In the above expression format, for example, (meth) acrylic acid represents acrylic acid and / or methatalic acid.

[0032] The method for synthesizing the (meth) acrylic acid ester polymer is not particularly limited, and may be performed by a known method. However, a polymer obtained by a normal free radical polymerization method using an azo compound or a peroxide as a polymerization initiator has a problem that the molecular weight distribution value is generally 2 or more and the viscosity becomes high. ing. Therefore, it is a low-viscosity (meth) acrylate polymer having a narrow molecular weight distribution and a high molecular weight (meth) acrylate polymer having a crosslinkable functional group at the end of the molecular chain. In order to obtain a coalescence, it is preferable to use a living radical polymerization method.

[0033] Among the “living radical polymerization methods”, an “atom transfer radical polymerization method in which (meth) acrylate monomers are polymerized using an organic halide or a halogenated sulfonyl compound as an initiator and a transition metal complex as a catalyst. In addition to the characteristics of the “living radical polymerization method” described above, the terminal has a halogen or the like that is relatively advantageous for functional group conversion reaction, and has a large degree of freedom in designing initiators and catalysts. The method for producing a (meth) acrylic acid ester polymer having a functional group is more preferable. Examples of this atom transfer radical polymerization method include Matyjaszewski et al., J. Am. Chem. Soc. 1995, 117, 5614.

[0034] Examples of a method for producing a (meth) acrylic acid ester-based polymer having an alkenyl group include a method using an atom transfer radical polymerization method disclosed in JP-A-9-272714 and the like, and a chain transfer agent. However, it is not particularly limited to these.

[0035] In order to obtain a cured product, at least one alkenyl group needs to be present in the molecule of the organic polymer (A). If the number of alkenyl groups is less than 1, the curability will be insufficient. The When using a cured product as an adhesive, the number of alkenyl groups in one molecule is preferably 1 to 5 because it is necessary to make the cured product flexible; preferable.

[0036] The compound (B) containing at least one hydrosilyl group in one molecule in the present invention can be used without particular limitation as long as it has a hydrosilyl group. Examples of such compounds include orthohydropolyene polysiloxanes modified with organic groups from the viewpoint of availability of raw materials and compatibility with the organic polymer (A). These hydrosilyl group-containing compounds (B) preferably have good compatibility with the organic polymer (A). In particular, when the viscosity of the entire system is low, use of a material having low compatibility may cause phase separation and cause poor curing. Specifically, the structure of such an organohydropolyene polysiloxane is, for example,

[0037] [Chemical 2]

[0038] (where 2 ≤ b + c ≤ 50, l ≤ b ≤ 3, 0 ≤ c. R is a hydrocarbon group having 2 to 20 carbon atoms in the main chain and one or more phenyl groups. Group may be contained),

[0039] [Chemical 3]

[0040] (where 0≤d + e≤50, 0≤d≤l, 0≤e. R is a hydrocarbon group having 2 to 20 carbon atoms in the main chain and one or more phenyl groups. Group), or

[0041] [Chemical 4] CH ₃

Hubby f 9

[0042] (where 3≤f + g≤20, l≤f≤S CRII 3, 0≤g <18. R is a hydrocarbon group having 2 to 20 carbon atoms in the main chain. A chain or cyclic group represented by the above-mentioned (which may contain a phenyl group).

[0043] Specific examples of the hydrosilyl group-containing compound (B) having relatively good compatibility with the organic polymer (A) and the hydrosilyl group-containing compound (B), or dispersion stability and curing rate are as follows. Can be mentioned.

[0044] [Chemical 5]

[0045] (where l≤k≤3, 0≤1≤8, and R is a hydrocarbon group having 8 or more carbon atoms.)

As a more specific example of the hydrosilyl group-containing compound (B), methyl-nodrodiene polysiloxane is used in order to ensure compatibility with the organic polymer (A) and to adjust the amount of SiH. Examples include compounds modified with α-methylstyrene, arylalkyl ether, arylalkyl ester, arylphenyl ether, arylphenyl ester, and the like, and examples thereof include the following structures.

[0046] [Chemical 6

[0047] (In the above formula, l≤p≤3, l≤q≤8.)

The blending amount of the hydrosilyl group-containing compound (B) with respect to the organic polymer (A) is such that the hydrosilyl group content of the hydrosilyl group-containing compound (B) is 0.3 with respect to 1 equivalent of the aryl group of the organic polymer (A). It is preferably ˜5.0 equivalents. When the amount of hydrosilyl group is less than 0.3 equivalent, a sufficient cured product may not be obtained. On the other hand, when it exceeds 5.0 equivalent, excess hydrosilyl group-containing compound (B) is used as a plasticizer component. work, sometimes force ^s detract from the physical properties of the cured product.

[0048] The hydrosilylation catalyst (C) of the present invention is not particularly limited, and any catalyst can be used. For example, solid platinum supported on a carrier such as chloroplatinic acid, platinum alone, alumina, silica, carbon black, etc .; platinum-bulusiloxane complex {eg, Pt

(ViMe SiOSiMe Vi), Pt [(MeViSiO)]}; platinum phosphine complex {eg, Pt

X 2 2 y 4 z

(PPh), Pt (PBu)}; platinum phosphite complex {eg Pt [P (OPh)], Pt [P (

3 4 3 4 3 4

OBu)] (wherein Me is a methyl group, Bu is a butyl group, Vi is a buyl group, Ph is a phenyl group

3 4

X and z represent integers), Pt (acac) (where acac represents acetylylacetonate), and platinum hydrocarbons described in Ashby et al. US Pat. Nos. 3,159,601 and 31,596,62. Also included are composites and platinum alcoholate catalysts described in US Pat. No. 3,220,972 to Lamoreaux et al.

[0049] Examples of catalysts other than platinum compounds include RhCl (PPh), RhCl, Rh / Al 2 O 3

3 3 3 2 3

, RuCl, IrCl, FeCl, A1C1, PdCl · 2H〇, NiCl, TiCl, etc. This

3 3 3 3 2 2 2 4

These catalysts may be used alone or in combination of two or more. Special amount of catalyst used Limit it! / In, but is preferably used in the range of 10- ⁸ ~ 10- imol respect alkenyl group lmol in component (A). Preferably 10- ⁶ to; it is employed in the range of 10- ² mol. 10- ⁸ mol Not Mitsurude, it is likely to become unstable curing rate Osogu The curable. Conversely, if it exceeds 10-ol, it is not preferable because it is difficult to ensure pot life.

[0050] From the viewpoints of availability and catalytic activity, chloroplatinic acid and platinum butylsiloxane are particularly preferred. No particular limitation is imposed on the amount of the catalyst used, is employed in the range of 6 X 10- ⁴ ~3 X 10- ³ parts by weight as a metal amount of the organic polymer (A) preferably. 6 X 10- ⁴ is less than parts by weight, is likely to become unstable hardening rate Osogu The curable. 3 X 10- ³ when the parts Eru Yue conversely, tends to give heat resistance in addition to the cured product is colored, the adverse weathering.

[0051] The compound (D) used in the present invention is generally known as a hindered amine compound, and can be used without particular limitation as long as it acts as a radical scavenger. The compound (D) is distributed to the hydrosilylation catalyst (C). Those containing atoms having a high potential are not preferable because a sufficient cured product cannot be obtained by deactivating the hydrosilylation catalyst and inhibiting the hydrosilylation reaction. P, Sn, etc. are known as atoms that inhibit the hydrosilylation reaction.

[0052] It is known that hindered amine compounds are suitably used as light stabilizers.

The 1S N atom is also generally an inhibitor of the hydrosilylation reaction. However, even a hindered amine compound has a tertiary amino group and does not have a primary amino group, secondary amino group or nitryl group, that is, N in the following general formula (1) If the atom bonded to the atom is the same, it is possible to obtain a cured product that has a small effect on the curability of the compound cured by the hydrosilylation reaction, and is extremely good as a light stabilizer. Show characteristics

Yes

[0053] [Chemical 7]

[0054] X in the general formula (1) is an organic group in which the atom bonded to N is C. Examples of the organic group include alkyl groups such as a methoxy group and an ethoxy group, and an acyl group. It is done. Preferably, it is an acyl group, and since the basicity of the compound is low, a good cured product can be obtained without reducing the reaction rate of hydrosilylation. In the general formula (1), R ^u , R ¹² , R ¹³ , and R ¹⁴ represent an alkyl group having 1 to 8 carbon atoms, and each may be the same or different. R ^U , R ¹² , R ¹³ and R ¹⁴ are preferably a methoxy group, an ethoxy group, or a t-butoxy group.

[0055] Specific examples of the compound (D) include Sanol LS-765 manufactured by Sankyo Lifetech Co., Ltd., Adeka Stub LA-63 manufactured by Asahi Denka Kogyo Co., Ltd., and examples of compounds having an acyl group manufactured by Clariant 'Japan Co., Ltd. Sanduvor3058Liq is exemplified.

[0056] In the curable composition of the present invention, the compound) is preferably 0.0;! To 20 parts by weight, more preferably 0.01 to 10 parts per 100 parts by weight of the organic polymer (A). Part by weight, particularly preferably from 0.03 to 5 parts by weight is used. If the content of the compound (D) is less than 0.01 parts by weight, the weather resistance improving effect may deteriorate. On the other hand, if it exceeds 20 parts by weight, the curability and physical properties of the cured product (for example, strength at break and elongation) may be lowered.

[0057] An ultraviolet absorber can be added to the curable composition of the present invention for the purpose of further improving the weather resistance. As the ultraviolet absorber, various known ultraviolet absorbers such as a benzotriazole ultraviolet absorber and a benzophenone ultraviolet absorber can be used as long as they do not inhibit the hydrosilylation reaction.

[0058] In addition, a storage stability improver can be used in the curable composition of the present invention for the purpose of improving storage stability. This storage stability improver includes hydrosilylation reaction. It is not particularly limited as long as it is a normal stabilizer known as a storage stabilizer and can achieve the intended purpose. Specifically, a compound containing an aliphatic unsaturated bond, an organic phosphorus compound, an organic sulfur compound, a nitrogen-containing compound, a tin compound, an organic peroxide, or the like can be suitably used. Specifically, 2-benzothiazolyl sanolide, benzothiazole, thiazole, dimethylacetylene dicarboxylate, jetylacetylene dicarboxylate, 2,6 di-tert-butyl-4-methylphenol, butylhydroxyanisole, vitamin E, 2- (4 morphodinyldithio) benzothiazole, 3-methyl-1-butene-3-ol, acetylenically unsaturated group-containing organosiloxane, acetylene alcohol, 3-methyl-1-butyl-3-ol, diarino refumarate, diarino Examples include, but are not limited to, remaleate, jetinorefumarate, jetinoremaleate, dimethylmaleate, 2-pentenenitryl, and 2,3 dichroic propene.

[0059] Further, the curable composition of the present invention is added with an adhesion-imparting agent for improving the adhesion to various supports (metal core, plastic film, metal foil, paper, etc.) as necessary. That power S. Examples of the adhesion imparting agent include various silane coupling agents and epoxy resins. In particular, a silane coupling agent having a functional group such as an epoxy group, a methacryloyl group, or a bur group is easy to use because it has a small effect on curability and a large effect on expression of adhesiveness. However, usable silane coupling agents are not limited to these. In addition, a catalyst for reacting a silyl group or an epoxy group can be added in combination with a silane coupling agent or an epoxy resin. In their use, the impact on the hydrosilylation reaction must be considered.

[0060] In addition, various fillers, antioxidants, pigments, surfactants, solvents, and silicon compounds may be appropriately added to the curable composition of the present invention. Specific examples of the filler include fine silica powder, calcium carbonate, clay, talc, titanium oxide, zinc white, diatomaceous earth, and barium sulfate.

[0061] Furthermore, when used as a pressure-sensitive adhesive, a tackifying resin can be added as necessary in order to improve the properties such as pressure-sensitive adhesive strength. Examples of the tackifying resin include terpene resin, terpene phenol resin, petroleum resin, rosin ester, and the like. It can be freely selected according to the application.

[0062] From the viewpoint of improving characteristics, resins such as phenol resin, acrylic resin, styrene resin, and xylene resin can be added. It is also possible to add adhesive components such as acrylic adhesive, styrene block adhesive, and olefin adhesive for the same purpose.

[0063] In the present invention, the curable composition is cured by the addition reaction of the Si-H group to the alkenyl group using the hydrosilylation catalyst, so that the curing rate is high, and thus the productivity is high. In addition, since no by-product is generated during the reaction during curing, it is possible to produce a cured product that is uniform and free of bubbles.

[0064] Examples of the method for producing the curable composition of the present invention include LIM molding and a pressure-sensitive adhesive processing method using a heating furnace as long as the method is a method of heat-curing the curable composition.

[0065] The method of thermosetting is not particularly limited, but the temperature varies depending on the polymer used and the kind of the compound to be added. Usually, the temperature is preferably in the range of 50 ° C to 180 ° C. The curing time varies depending on the polymer to be used, the compound to be added, the reaction temperature, etc., but usually 0.1 minute to 24 hours, preferably 30 seconds to 10 hours, more preferably 30 seconds to 30 minutes. It is.

[0066] The curable composition of the present invention is used as a molded body for rubber rollers, packing, vibration-proof materials, and the like. Adhesive materials include: packaging adhesive tapes, office adhesive tapes, paint masking tapes, electrical insulating adhesive tapes, binding adhesive tapes, protective adhesive tapes, identification adhesive tapes and sheets for decoration, double-sided adhesive tapes, Electromagnetic interference prevention film and tape, re-peeling film and tape, decorative board film, semiconductor chip transport tape, marking film, protective film for deep drawing, glass shatterproof film, foam adhesive tape, waterproof It can be used for water-stopping tapes, anticorrosion adhesive tapes, surface protective adhesive tapes, dicing adhesive tapes, back grind adhesive tapes, printing adhesive sheets, adhesive labels, and the like.

Example

[0067] Next, the composition of the present invention will be specifically described by way of examples, but the present invention is not limited to these examples. [0068] (Production Example 1)

Propylene oxide starting with a 3,000-hydroxypropylene polymer darlycol polymerized using a complex metal cyanide complex catalyst (zinc hexocyanobaltate) and caustic alkali as catalyst. The number average molecular weight of the terminal hydroxyl group is 28,000 (Tosoh's HLC-8120GPC is used as the liquid feeding system, Tosoh's TSK-GEL H type is used as the liquid feeding system, and THF is used as the solvent. Thus, an oxypropylene polymer having a molecular weight measured in terms of polystyrene) was obtained. In the same manner as in Synthesis Example 1 of JP-A-5-117521, the obtained oxypropylene polymer was subjected to a hydroxyl group at its terminal using a 28% methanol solution of Nato BR> gata E methylate and allylic chloride. Was converted to an aryl group and then desalted and purified to obtain a polyoxyalkylene polymer (A-1) having approximately two aryl ends in one molecule. The amount of the aryl terminal group of the obtained polyoxyalkylene polymer (A-1) having an aryl terminal was 0 · 12 mmol / g (measured by titration of the aryl group by a method based on JIS K 1557). It was.

[0069] (Production Example 2)

(One Si—O1) 0.5 equivalent of α-methylstyrene of the total amount of hydrosilyl groups in the presence of a platinum catalyst was added to methylhydrogen silicone having an average of 5 repeating units, and an average of 2 in one molecule. A compound (Β-1) having 5 hydrosilyl groups was obtained. This compound (Si-1) had a Si-Η group content of 3.2 mmol / g (the amount of hydrogen generated by adding the compound to 30% ethanolic potassium hydroxide was measured with a WS-type wet gas meter, The Si—H group content of the product was estimated).

[0070] (Production Example 3)

In the presence of platinum catalyst, 0.5 equivalent of α-methylstyrene of the total amount of hydrosilyl groups is added to methylhydrogen silicone with an average of 10 (one Si—O—) repeating units, and an average of 5 units per molecule. The compound (Β-2) having a hydrosilyl group was obtained. The Si—H group content of this compound was 4.2 mmol / g.

[0071] (Examples;! To 7, Comparative examples;! To 6)

The formulations shown in Table 1 were stirred for 1 hour while degassing to prepare each curable composition. The resulting curable composition was applied to a thickness of lmm, cured at 130 ° C for 5 minutes, and then 60 ° C. It was completely cured by leaving it in an oven for 24 hours to obtain a colorless and transparent cured product sheet having a thickness of 1 mm.

[table 1]

λ 鳞 ¾ 鹑 s¾) 26

* 1: Irganox 1010 (Chipa 'Specialty' Chemicals)

* 2: 3% isopropanol solution of platinum bursiloxane. The amount of platinum metal in the parentheses in the table.

* 3: 2-Methyl-3-butyne-2ol (manufactured by Wako Pure Chemical Industries, Ltd.)

* 4: Hostavin PR-25 Gran (manufactured by Clariant Japan Co., Ltd.)

[0073] The hindered amine compounds (Sanol LS765 and Sanduvor 3058 Liq.) Used in Examples;! To 7 and the hindered amine compounds (Sanol LS770 and TINUVIN 123) used in Comparative Examples 5 and 6 are , Each having the following chemical structure.

[0074] [Chemical 8

Sanol LS765

[0075] [Chemical 9]

Sanduvor 3058 Liq.

[0076] [Chemical 10]

SANOR LS770

[0077] [Chemical 11] TINUVIN 123

[0078] Further, Hostavin PR-25 Gran. Used as an ultraviolet absorber in Examples 4 and 5 is assumed to have the following chemical structure!

[0079] [Chemical 12]

Hostavin PR-25 Gran.

[0080] Table 2 shows the evaluation results of the weather resistance, heat resistance, and discoloration of the obtained cured sheet, and the evaluation results of the initial curability at the time of curing. Each evaluation of weather resistance, curability, heat resistance, and discoloration was performed as follows.

(Weather resistance test)

The cured product sheet obtained above is irradiated with a sunshine weatherometer (Suga Test Instruments WEL — SUN — DC type, black panel temperature 63 ° C), and the time until the cured product softens (unit: hours) ) Was measured.

(Evaluation of curability)

The surface of the cured product when heated and cured at 130 ° C for 5 minutes was touched with a finger to confirm the degree of cure! /. With the cured product obtained by thermosetting the curable composition of Comparative Example 1 as a standard (◯), The cured product was evaluated as follows.

[0081] A: Comparative example 1 or more

○: Equivalent to Comparative Example 1

○ △: slightly inferior to Comparative Example 1

X: Uncured

(Evaluation of heat resistance)

The obtained cured sheet was stored at 100 ° C for 1000 hours, and the degree of heat deterioration was confirmed by comparing the appearance of the cured sheet and the tackiness of the surface with those before the heat test. The cured sheet of Comparative Example 1 after storage at 100 ° C. was used as a standard (◯), and each cured sheet was evaluated as follows.

[0082] A: Comparative example 1 or more

○: Equivalent to Comparative Example 1

○ △: slightly inferior to Comparative Example 1

X: Uncured

(Evaluation of discoloration)

The obtained cured sheet was visually checked for discoloration over time during the heat resistance test. Each evaluation was performed as follows.

[0083] ○: No discoloration

Δ: Transparent but colored

X: There is coloring

[0084] [Table 2]

* 1: The physical properties could not be evaluated because a cured product could not be obtained.

Examples: As shown in! To 7, the cured product to which the compound (D) of the present invention was added was compared with the cured product to which the compound (D) was not added as shown in Comparative Examples 1 to 4, Extremely excellent weather resistance.

Claims

The scope of the claims

[1] Organic polymer (A) having at least one alkenyl group in one molecule,

Compound (B) having at least one hydrosilyl group in one molecule,

[2] The curable composition according to claim 1, wherein the compound (D) is a compound in which one N atom is present in the cyclic skeleton and / or a compound in which two N atoms are present in the cyclic skeleton. object

[3] The curable composition according to claim 1, wherein the compound (D) is a 5-membered ring and / or a 6-membered ring having 1 N atom.

[4] The curable composition according to claim 1, wherein the compound (D) is a 5-membered ring and / or a 6-membered ring having two N atoms.

[5] The curable composition according to any one of claims 1 to 4, wherein the compound (D) has an alkyl group having 1 to 18 carbon atoms on at least one carbon atom constituting the cyclic skeleton. object.

[6] The compound (D) has the following general formula (1) in the molecule:

[Chemical 1]

(Wherein X is an organic group in which the atom bonded to N is C, R ^u , R ¹

R ¹⁴ represents an alkyl group having 1 to 8 carbon atoms, and each may be the same or different. )

The curable composition according to claim 1, wherein the content is 0.0;! To 20 parts by weight with respect to 100 parts by weight of the organic polymer (A). .

[7] The main chain of the organic polymer (A) is essentially polyoxyalkylene or poly (meth) attaly. The curable composition according to claim 1, which is a rate.

8. The curable composition according to claim 7, wherein the main chain of the organic polymer (A) is essentially polyoxypropylene.

[9] The curable composition according to any one of claims 6 to 8, wherein X in the general formula (1) is an acyl group.

10. The curable composition according to any one of claims 1 to 9, wherein the hydrosilylation catalyst (C) is chloroplatinic acid and / or platinum butylsiloxane.

[11] The metal content of the hydrosilylation catalyst (C) is the organic polymer (A) for the 100 parts by weight of 6 X 10- ⁴ ~3 X 10- ³ parts by weight, according to claim 10 Curable composition.

[12] The content of the compound (D) is 0.01-2 with respect to 100 parts by weight of the organic polymer (A).

The curable composition according to claim 1, which is 0 part by weight.