WO2006106929A1

WO2006106929A1 - Resin composition and molded object

Info

Publication number: WO2006106929A1
Application number: PCT/JP2006/306851
Authority: WO
Inventors: Kyoichi Kubomura; Takehiko Nishijima
Original assignee: Zeon Corporation
Priority date: 2005-03-31
Filing date: 2006-03-31
Publication date: 2006-10-12
Also published as: JPWO2006106929A1; JP4985397B2

Abstract

A resin composition having even better transparency and resistance to high temperatures and high humidities; and a molding obtained by molding the composition. The resin composition is characterized in that it comprises a vinylalicyclic hydrocarbon polymer (A) and a product (B) of the hydrogenation of an aromatic vinyl/conjugated diene block copolymer (b), and that 1) the aromatic vinyl/conjugated diene block copolymer (b) before the hydrogenation comprises a polymer block (i) consisting of repeating units derived from an aromatic vinyl compound and a polymer block (ii) consisting of repeating units derived from a conjugated diene compound, 2) the polymer block (ii) has repeating units formed by 1,2-addition polymerization and 3,4-addition polymerization in a total amount of 40 wt.% or more based on the repeating units derived from a conjugated diene compound and constituting the block (ii), and 3) the block copolymer has a hydroxy group at an end of the backbone thereof.

Description

Specification

Resin composition and molded body

Technical field

[0001] The present invention relates to a resin composition and a molded body, and more particularly to a resin composition excellent in transparency and high temperature and humidity resistance and a molded body formed by molding the same.

Background art

[0002] Vinyl alicyclic hydrocarbon polymers are excellent in transparency, low hygroscopicity, chemical resistance, heat resistance, and low birefringence, and are used in optical members such as lenses and optical disk substrates. . However, a molded body consisting only of a vinyl alicyclic hydrocarbon polymer may become cloudy (inferior in high-temperature and high-humidity resistance) if it is placed in a high-temperature and high-humidity environment for a long time and then suddenly placed at room temperature. is there. Accordingly, attempts have been made to improve the high temperature and high humidity resistance by adding a compounding agent to the bur cycloaliphatic hydrocarbon polymer. For example, Patent Literature 1 and Patent Literature 2 disclose a resin composition in which a soft polymer such as styrene butadiene styrene block copolymer is blended with a vinyl alicyclic hydrocarbon polymer, and molding the same. Thus, it has been disclosed that small lenses such as pickup lenses having transparency and high temperature and high humidity resistance at practical levels can be obtained.

[0003] Patent Document 1: Japanese Unexamined Patent Application Publication No. 2002-148401

Patent Document 2: US Patent No. 6965003

Disclosure of the invention

Problems to be solved by the invention

[0004] Since a lens made of resin is easy to use and lightweight, it is necessary to use a large lens such as a projector lens or a camera lens that connects the resin lens only with a small lens such as a pick-up lens. Application to imaging lenses is being studied. Large lenses with excellent transparency and no fogging are required for imaging lenses.

However, when a large image lens is molded with a greave composition containing a bull alicyclic hydrocarbon polymer and a soft polymer described in Patent Documents 1 and 2, the lens may be slightly clouded. . The present inventor has investigated the cause of the cloudiness of the lens, patent document 1 However, although the high-temperature and high-humidity resistance is at a practical level, it has been proved that the transparency is insufficient for large lenses.

In view of the above situation, an object of the present invention is to provide a resin composition that is more excellent in transparency and high-temperature and high-humidity resistance, and a molded body using the same.

Means for solving the problem

[0005] The present inventor has intensively studied a soft polymer to be blended with the vinyl alicyclic hydrocarbon polymer (A) that achieves the above object, and as a result, has a hydroxyl group at the end of the main chain, and An aromatic bule-conjugated gen block copolymer (b) having a specific proportion or more of a repeating unit obtained by 1,2-addition polymerization or 3,4-addition polymerization of a conjugated genji compound at a specific ratio. By using the hydrogenated product (B) as a soft polymer, it is possible to obtain a large lens that is remarkably excellent in transparency and that does not cause white turbidity even when returned to room temperature after being left under high temperature and high humidity. I found it. The present inventor has further studied based on these findings and has completed the present invention.

[0006] Forcibly, the present invention comprises a bur alicyclic hydrocarbon polymer (A) and a hydride (B) of an aromatic bur-conjugated gen block copolymer (b),

The aromatic vinyl-conjugated gen block copolymer (b) before hydrogenation is

1) It consists of a polymer block (i) having a repeating unit force derived from an aromatic beryl compound and a polymer block (ii) having a repeating unit force derived from a conjugated gen compound.

2) The polymer block (ii) has 40% by weight or more of 1,2-addition-polymerized and 3,4-addition-polymerized repeating units in the repeating units derived from the conjugation compound constituting it, And

3) It has a hydroxyl group at the end of the main chain,

It is a rosin composition characterized by the above-mentioned.

Moreover, this invention is a molded object formed by shape | molding this resin composition.

The invention's effect

[0007] The resin composition of the present invention is remarkably excellent in transparency and high temperature and high humidity resistance. Large lenses obtained by molding this resin composition have no haze.

The reason why a large lens without cloudiness can be obtained by the rosin composition of the present invention is clear. Although not a certain amount of branched structure in the molecular chain of polymer block (Π) in polymer (B) or hydride (B) (1,2-addition polymerization or 3,4-addition of conjugated gen compounds) (Repeating units formed by polymerization) reduce the cohesive energy density, and can uniformly disperse the polymer (B) or hydride (B) in the polymer (A), forming a very small size domain. Therefore, it is considered that the transparency is remarkably improved.

In addition, the hydroxyl group at the end of the polymer (B) or hydride (B) prevents agglomeration of moisture that has been absorbed, and suppresses the generation of microcrazes. It is considered that white turbidity does not occur even if it is returned to.

BEST MODE FOR CARRYING OUT THE INVENTION

[0008] The resin composition of the present invention comprises a bur cycloaliphatic hydrocarbon polymer (A) and a hydride (B) of an aromatic bur-co-functional genblock copolymer (b). And

The aromatic vinyl-conjugated gen block copolymer (b) before hydrogenation is

3) It has a hydroxyl group at the end of the main chain.

[0009] (Vinyl alicyclic hydrocarbon polymer (A))

The vinyl alicyclic hydrocarbon polymer (A) used in the present invention is a repeating unit obtained by vinyl addition polymerization of a vinyl alicyclic hydrocarbon compound, that is, a repeating chain having an alicyclic structure in the side chain. A polymer having units. The repeating unit derived from the vinyl alicyclic hydrocarbon compound is usually contained in the polymer in an amount of 50% by weight or more, preferably 70% by weight or more, more preferably 80% by weight or more. The repeating unit derived from the vinyl alicyclic hydrocarbon compound has the same structure as the repeating unit obtained by bulle addition polymerization of the bur alicyclic hydrocarbon compound. It shall then contain repeat units obtained by hydrogenating the aromatic ring.

[0010] The number of carbon atoms constituting the alicyclic structure is usually 4 to 30, preferably 5 to 20, more preferably. Preferably it is in the range of 5-15, most preferably 6. When the number of carbon atoms constituting the alicyclic structure is within this range, the heat resistance and molding processability of the obtained rosin composition and the mechanical strength of the obtained molded body are excellent.

[0011] The glass transition temperature (Tg) of the polymer (A) used in the present invention is preferably 80 to 250 ° C, more preferably 90 to 200 ° C, and particularly preferably 100 to 150 ° C. is there. In the polymer (A) obtained by block copolymerization, it is usually preferable that the Tg on the high temperature side is in the above range. When Tg is in the above range, the resulting molded article is excellent in the balance between strength characteristics and heat resistance, and the molding processability of the obtained resin composition.

In the present invention, the glass transition temperature (Tg) is a value measured using a differential scanning calorimeter under conditions of 10 ° CZ.

[0012] The weight average molecular weight (Mw) of the polymer (A) is preferably 10,000 to 500,000, more preferably <30,000 to 350,000, and even more preferably <50,000 to 200 , 000. If the Mw force is too large, the strength characteristics of the resulting molded article are inferior. If it is too large, the moldability of the obtained resin composition is inferior, and the birefringence of the obtained molded article increases. An increase in birefringence is not preferable because defects such as rainbow-like color distortion occur in an image viewed through the molded body. In the present invention, the weight average molecular weight (Mw) is a polystyrene equivalent value measured by gel permeation chromatography (GPC).

[0013] The molecular weight distribution (MwZMn) of the polymer (A) is preferably 5 or less, more preferably 4 or less, particularly preferably 3 or less, and most preferably 2 or less. If this MwZMn is too large, the mechanical properties and heat resistance of the resulting molded product will be reduced. In particular, Mw ZMn is more preferably 2 or less, more preferably 1.7 or less, in order to achieve a high balance between the mechanical strength, heat resistance, and moldability of the obtained resin composition. Masug 1. 5 or less is most preferable. In the present invention, the number average molecular weight (Mn) is a polystyrene equivalent value measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent.

[0014] In order to bring the MwZMn of the polymer (A) into the above preferred range, a living polymerization method such as living-on polymerization is preferable among the above polymerization methods. For example, living-on polymerization is usually performed in the presence of a polymerization initiator at 0 ° C to 150 ° C, preferably 10 ° C to 100 ° C. Particularly preferred is a temperature range of 20 ° C to 80 ° C. Examples of the initiator include monoorganolithium such as n-ptyllithium, sec butyllithium, t-butyllithium, hexyllithium, and ferrous lithium, dilithiomethane, 1,4-dilithibutane, 1,4-dilithium-2-ethylcyclohexane, and the like. Examples include functional organolithium compounds.

[0015] Such a polymer (A) includes an addition polymer of a saturated alicyclic vinyl compound, an addition polymer of an unsaturated alicyclic vinyl compound, a hydride thereof, and an addition polymer of an aromatic vinyl compound. Aromatic ring hydrides and the like can be mentioned.

[0016] Examples of the saturated alicyclic butyl compound include butylcyclohexane, 3-methylisopropylcyclohexane, and those having a substituent such as a halogen group, an alkoxy group, and a hydroxyl group.

[0017] Examples of the unsaturated alicyclic bur compound include 4 bulucyclohexene, 4 isopropyl hexene, 1-methyl-4 burcyclohexene, 2-methyl-4 burcyclo hexene, 1-methinoleole 4 isopropenylcyclohexene. 2-methylolene 4 iso-propylcyclohexene, and those having a substituent such as a halogen group, an alkoxy group or a hydroxyl group.

[0018] Examples of the aromatic bur compound include styrene, at-methyl styrene, at-ethyl styrene propino styrene, α isopropylino styrene, α-tert butyl styrene, 2-methylol styrene, 3-methino styrene, 4-methino styrene. Restyrene, 2,4 Diisopropylstyrene, 2,4 Dimethylstyrene, 4-t-Butylstyrene, 5-t Butyl-2-methylstyrene, 4-Monochlorostyrene, Dichlorostyrene, 4-Monophenolostyrene, 4-Phenylstyrene, These And those having a substituent such as a halogen group, an alkoxy group, and a hydroxyl group.

[0019] These saturated alicyclic vinyl compounds, unsaturated alicyclic vinyl compounds, and aromatic vinyl compounds can be used alone or in combination of two or more.

[0020] The polymer (A) used in the present invention is a copolymerizable monomer other than a saturated alicyclic vinyl compound, an unsaturated alicyclic vinyl compound and an aromatic vinyl compound within a range of 50% by weight or less. It may have a repeating unit derived from a monomer. As copolymerizable monomer Includes a linear vinyl compound, a linear conjugated conjugated compound, and the like. The linear vinyl chloride compound and the linear conjugated gene compound may be those in which the straight chain is branched.

[0021] Examples of the linear bur compound include chain olefins such as ethylene, propylene, 1-butene, 1 pentene, 4-methyl-1 pentene, and among them, ethylene, propylene, and 1-butene are most preferable.

[0022] Examples of the linear conjugation compound include 1,3 butadiene, 1,2 butadiene, isoprene, 2,3 dimethyl-1,3 butadiene, 1,3 pentagen, and 1,3 hexadiene. It is done. Of these linear vinyl icy compounds and linear conjugated gens, 1,3 butadiene and isoprene are particularly preferred, with linear conjugated genic compounds being preferred. These linear vinyl compounds and linear conjugates can be used alone or in combination of two or more.

[0023] The polymer (A) is obtained by radical polymerization, anion polymerization, cation polymerization, living cation polymerization, living cation polymerization, coordination cation polymerization, coordination cation polymerization, or living radical polymerization. It can be obtained by homopolymerization or copolymerization using a known polymerization method such as the above, and hydrogenating as necessary.

[0024] The polymer (A) is not limited by the form of copolymerization and may be any of a random copolymer, a pseudo-random copolymer, a block copolymer, a gradient block copolymer, and the like. The polymer (A) obtained by block copolymerization is not limited by the number of blocks. For example, diblock structure, triblock structure, tetrablock structure, pentablock structure, hexablock structure, heptablock structure, etc. Is mentioned. Also, the block lengths of each block are the same or different!

[0025] In addition, the polymer (A) obtained through addition polymerization of an aromatic bur compound has a hydrogenation rate of all carbon-carbon unsaturated bonds containing an aromatic ring of usually 80 mol% or more, preferably 95 More than mol%, more preferably 99 ~: LOO mol%. That is, in the polymer (A) obtained through addition polymerization and hydrogenation of an aromatic bur compound, the ratio of the repeating unit having an aromatic ring is such that the repeating unit having an alicyclic structure and the repeating unit having an aromatic ring are Is usually 20 mol% or less, preferably 5 mol% or less, more preferably 1 mol% or less. [0026] The steric configuration of the polymer (A) used in the present invention may be any of atactic, isotactic, and syndiotactic. For example, the syndiotacticity by diamond display is 0 to 100%. Things can also be used.

[0027] The polymerization can be performed using a method such as solution polymerization or slurry polymerization. In consideration of removal of reaction heat, solution polymerization is preferable. In solution polymerization, an inert solvent that can dissolve the polymer and its hydride is used. Inert solvents include n-butane, n-pentane, isopentane, n-hexane, n-heptane, isooctane and other aliphatic hydrocarbons; cyclopentane, cyclohexane, methylcyclopentane, methylcyclohexane, Decalin, bicyclo [4.3.0] nonane, tricyclo [4.3.0.I ² ' ⁵ ] decane and other alicyclic hydrocarbons; benzene, toluene and other aromatic hydrocarbons, etc. Among these, alicyclic hydrocarbons are preferable because they can be used as they are as an inert solvent in the hydrogenation reaction. These inert solvents can be used alone or in combination of two or more, and are usually used at a ratio of 200 to 2,000 parts by weight with respect to 100 parts by weight of all monomers used. .

[0028] (Hydrolyzed aromatic bule conjugated gen block copolymer (b) (B))

The hydride (B) of the aromatic vinyl-conjugated gen block copolymer (b) used in the present invention is a hydrogenated aromatic vinyl-conjugated gen block copolymer (b). Of the aromatic bulle-conjugated genblock copolymer (b)

3) It has a hydroxyl group at the end of the main chain.

[0029] The aromatic belief compound constituting the polymer block (i) of the copolymer (b) includes styrene, a-methylstyrene, 1-burnaphthalene, p-methylstyrene, 4- Propylene, t-butyl styrene, 4-cyclohexyl styrene, 4-dodecyl styrene, 2-ethyl mono 4-benzyl styrene, 4- (phenylbutyl) styrene, dibutylbenzene, N , N-dimethyl-p-aminoethylstyrene, N, N jetyl-p-aminoethylstyrene, burpyridine and the like. Of these, styrene, which is preferably styrene and a-methylstyrene, is more preferable.

These aromatic vinyl compounds are used singly or in combination of two or more.

When two or more aromatic beryl compounds are used in combination, the polymer block (i), which is a repeating unit force derived from an aromatic vinyl compound, is a random copolymer of two or more aromatic bull compounds. It may be a block copolymer or a tapered copolymer.

[0030] Conjugated gene compounds constituting the polymer block (ii) of the copolymer (b) include 1,3-butadiene, isoprene, 2,3 dimethyl-1,3 butadiene, 1,3 pentene, 2 -Methyl-1,3 pentagen, 1,3 hexagen, 4,5 Jetyl-1,3-octadiene, 3-butyl-1,3-octadiene, black mouthplane and the like. Among these, 1,3 butadiene, isoprene, and 1,3 pentagen are preferable. 1,3 butadiene and isoprene are more preferable.

[0031] These conjugation compounds may be used alone or in combination of two or more.

When two or more kinds of conjugated genie compounds are used in combination, the polymer block (ii) having a repeating unit force derived from the conjugated gen compound is a random copolymerization of two or more kinds of conjugated genie compounds. Alternatively, it may be a block copolymer or a tapered copolymer.

[0032] The combination of the conjugation compound is not particularly limited, but a combination of isoprene and 1,3 butadiene is preferred.

In addition, when the conjugation compound combination is isoprene and 1,3 butadiene

The proportion of repeating units derived from isoprene in all repeating units of the conjugated gen block (ii) is preferably 60% or more.

[0033] The mode of the block of the aromatic bu-conjugated conjugated block copolymer (b) is not particularly limited, and examples thereof include diblocks, triblocks, and more multiblocks. Ingredients Specifically, polymer block (i) and polymer block (ii) force ((i) one (ii), (ii) one ((i) one (ii

)), ((I) (ii)) One embodiment of (i) is exemplified. Here, n is an integer of 1 or more. Among these, the aromatic bulle-conjugated gen block copolymer (b) having the block form represented by (i)-(ii)-(i) is preferred.

[0034] The ratio of the polymer block (i) in the polymer (b) is preferably 15 to 55% by weight, more preferably 20 to 50% by weight, and particularly preferably 25 to 45% by weight. is there.

[0035] The polymer block (ii) has 40% by weight or more of the repeating units derived from the conjugation compound composing it and the repeating units subjected to 1, 2 addition polymerization and 3, 4 addition polymerization. Yes. By having the content of 40% by weight or more, the transparency of the resin composition becomes more excellent.

Depending on the polymerization reaction site of the conjugated diene compound, the 1,2 addition polymerization-derived repeating unit, the 3,4 addition polymerization-derived repeating unit, and the 1,4-addition polymerization-derived repeating unit may be performed depending on the polymerization reaction site of the conjugated gen compound. One of these is formed. For example, when 2-methyl 1,3 pentagen is used as the conjugate compound, 1,2-addition polymerization forms a repeating unit represented by (1-methyl-1-1 (1-propylene)) ethylene, 4 Addition polymerization forms a repeating unit represented by 1 isopropyl-methyl 2-methylethylene, and 1,4-addition polymerization forms a repeating unit represented by 1,3 dimethyl-2-butylene. The In the polymer block (ii), the ratio of 1,2 addition polymerization and 3,4 addition polymerization repeating units in the repeating unit derived from the conjugate conjugated compound was determined by the infrared analysis method and the Morero method. Can be calculated.

[0036] The polymer (b) has a hydroxyl group at the end of the main chain. The polymer (b) should have a hydroxyl group at the end of the main chain, and usually has a hydroxyl group at 30% or more, preferably 50% or more, more preferably 70% or more of the end of the main chain. If it is.

[0037] The aromatic vinyl-conjugated gen block copolymer (b) used in the present invention can be polymerized by ion polymerization methods such as ion polymerization, cation polymerization, single site polymerization methods, radical polymerization methods, etc. It is obtained by forming the basic skeleton (main chain) of the union (b) and then converting the end of the main chain to a hydroxyl group.

For example, using an organic lithium compound as an initiator, such as n-hexane and cyclohexane A main chain having a desired molecular structure and molecular weight is formed by a sequential polymerization method in which an aromatic vinyl compound is polymerized in an inert organic solvent and then a conjugated diene compound is polymerized. Then, ethylene oxide, propylene oxide is formed. In addition, a compound having an oxysilane skeleton such as styrene oxide is added, and then an active hydrogen-containing compound such as alcohols, carboxylic acids and water is added to stop the polymerization.

[0038] The amount of terminal hydroxyl groups can be adjusted by the modification rate, and the modification rate can be adjusted by, for example, the amount of catalyst used for living anion polymerization and the amount of ethylene oxide used.

[0039] Examples of the organic lithium compound include monolithium compounds such as methyllithium, ethyllithium, pentyllithium, and butyllithium; dilithium compounds such as naphthalenedilithium and dilithihexylbenzene.

The proportion of the organolithium compound used is not particularly limited, but is usually 0.005 to 0.2 part by weight per 100 parts by weight of the monomer.

[0040] The polymerization reaction is preferably performed in a solvent.

The solvent is not particularly limited as long as it is an organic solvent inert to the polymerization initiator, and examples thereof include hexane, heptane, cyclohexane, methylcyclohexane, and benzene.

[0041] The reaction temperature of the polymerization reaction is not particularly limited, but is usually 0 to 80 ° C. The reaction time for the polymerization reaction is not particularly limited, but is usually 0.5 to 50 hours.

[0042] The proportion of repeating units derived from 1,2- and 3,4-addition polymerization in the repeating units derived from the conjugating compound in the conjugating block (ii) is determined during polymerization of the conjugating compound. It can be adjusted by using a Lewis base as a cocatalyst.

Lewis bases include ethers such as dimethyl ether, jetyl ether, and tetrahydrofuran; glycol ethers such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and ethylene glycol dibutyl ether; triethylamine, N, N, N ′, N ′ — And amine compounds such as tetramethylethylenediamine (TMEDA), pyridine, tribubutylamine, N-methylmorpholine, and the like.

These Lewis bases are usually used in an amount of 0.1 to 1 to 1 mol of lithium as a polymerization initiator. Used in the range of 000 moles.

[0043] The polymer (b) thus obtained can be hydrogenated to obtain the polymer (B) used in the present invention.

The method for hydrogenating the polymer (b) is not particularly limited, and for example, there is a method in which the polymer (b) is brought into contact with hydrogen in the presence of a hydrogenation catalyst in an inert organic solvent.

As the inert organic solvent, n-hexane, cyclohexane and the like are preferably used.

[0044] As the hydrogenation catalyst, Raney nickel or a heterogeneous catalyst such as Pt, Pd, Ru, Rh, Ni or the like supported on a carrier such as vigorous Bonn, alumina, diatomaceous earth, or a transition metal For example, a catalyst of a chidler system that has a combination force with an alkylaluminum compound or alkyllithium can be used. Of these, Ziegler catalysts consisting of alkylaluminum compounds and transition metals such as cobalt and nickel are preferred.

The hydrogen pressure during the hydrogenation reaction is preferably atmospheric pressure to 20 MPa, more preferably 0.1 to 15 MPa. The reaction temperature is preferably from room temperature to 250 ° C, more preferably from 20 to 150 ° C. The reaction time is preferably from 0.1 to L00 hours.

[0045] The hydrogenation rate of the carbon-carbon double bond in the polymer block (ii) is usually 60% or more, preferably 70% or more, more preferably 80% or more.

The hydrogenation rate of the aromatic ring in the polymer block (i) is usually less than 40%, preferably less than 30%, more preferably less than 10%, and most preferably less than 5%.

When the hydrogenation rate of the carbon-carbon double bond in the polymer block (ii) and the hydrogenation rate of the aromatic ring in the polymer block (i) are within this range, the transparency and mechanical properties of the resulting molded product Excellent strength, heat resistance, and weather resistance.

[0046] As described above, the hydride (B) of the aromatic bu-conjugated conjugated block copolymer (b) is obtained. This hydride (B) is composed of a polymer block (I) having a repeating unit derived from an aromatic beryl compound and a polymer block (有する) having a hydrogenated repeating unit derived from a conjugate conjugate compound. The polymer block (Π) consists of 1, 2 addition polymerization and 3, 4 addition polymerization repeating units among the hydrogenated repeating units derived from the conjugated pheny compound constituting the block (Π). And a polymer (B) having a hydroxyl group at the end of the main chain. [0047] The polymer (B) suitable for use in the present invention preferably has 30% or more, preferably 50% or more, particularly preferably 70% or more of hydroxyl groups at the ends of the main chain.

The polymer (B) suitable for use in the present invention is a polymer block (I) in the polymer (B).

) Is preferably 15 to 55% by weight, more preferably 20 to 50% by weight, particularly preferably

25 to 45 is in the range of weight ^_0/0.

[0048] The proportion of the hydrogenated repeating unit derived from the conjugated genie compound in the polymer block (Π) is determined by the hydrogenation of the conjugated geny compound! It is usually at least 60%, preferably at least 70%, more preferably at least 80%, based on the total amount with hydrogenated repeating units derived from the compound.

The repeating unit derived from the aromatic vinyl compound in the polymer block (I) is usually less than 40%.

Preferably comprising less than 30%, more preferably less than 10%, most preferably less than 5% of repeating units in which the aromatic ring is hydrogenated.

[0049] The glass transition temperature of the polymer (B) used in the present invention is usually 30 ° C or lower. When multiple Tg's are present, the polymer has the lowest Tg of 30 ° C or less.

[0050] (Coffin composition)

The resin composition of the present invention comprises the aforementioned polymer (A) and hydride (B) or polymer (B).

[0051] The ratio of the polymer (A) to the hydride (B) or the polymer (B) in the resin composition of the present invention is not particularly limited, but with respect to 100 parts by weight of the polymer (A), The hydride (B) or the polymer (B) is preferably 0.001 to 50 parts by weight, more preferably 0.01 to 10 parts by weight, and 0.05 to 5 parts by weight. Particularly preferred is 0.2 to 0.8 parts by weight.

[0052] The resin composition of the present invention comprises the refractive index (n (A)) of the polymer (A) used and the hydride used.

D

(B) or the difference in refractive index (n (B)) of the polymer (B) (I n (A) — n (B) |) is less than 0.01

D D D

It is preferable that (I n (A) -n (B) |) is less than 0.007.

D D

More preferably, it is 4 or less. (I n (A) -n (B) |)

D D

This means that the difference between the refractive index of (A) and the refractive index of the polymer hydride (B) used is small. When (I n (A) -n (B) |) is within this range, the transparency of the greave composition is more excellent. [0053] In the present invention, the refractive index is JIS K 0062 5. According to the method of measuring an individual sample,

It is a value measured at 25 ° C.

[0054] If necessary, other additives can be added to the resin composition of the present invention.

Other additives include, for example, antioxidants, light stabilizers, heat stabilizers, UV absorbers, near-infrared absorbers and other stabilizers; mold release agents, plasticizers and other resin modifiers; dyes, Colorants such as pigments; antistatic agents, light diffusing agents and the like can be mentioned.

[0055] Examples of the antioxidant are phenol-based antioxidants, phosphorus-based antioxidants, and phenol-based antioxidants. These antioxidants can be used alone or in combination of two or more. Of these, phenol-based anti-oxidants, particularly alkyl-substituted anti-oxidants can be suitably used. The addition amount of the antioxidant is preferably 0.01 to 2 parts by weight, more preferably 0.02 to 1 part by weight, based on 100 parts by weight of the polymer (A).

[0056] Examples of the light resistance stabilizer include hindered amine light resistance stabilizers (HALS) and benzoate light resistance stabilizers. These light stabilizers can be used alone or in combination of two or more. Of these, hindered amine light stabilizers can be used particularly suitably. The addition amount of the light-resistant stabilizer is preferably 0.01 to 2 parts by weight with respect to 100 parts by weight of the polymer (A), and more preferably 0.02 to 1 part by weight. More preferably, it is 0.05 to 0.5 parts by weight.

[0057] Examples of the release agent include «Raffins, naphthenes, aromatics, low molecular polyethylene wax, low molecular polypropylene wax, low molecular polystyrene wax or oxides thereof, carboxylic acid, hydroxyl group, ester group, etc. Denatured products such as hydrocarbon release agents; lauric acid, myristylic acid, palmitic acid, stearic acid, behenic acid, hydroxystearic acid, erucic acid, oleic acid, coconut fatty acid, phthalic acid, adipic acid, Fatty acid release agents such as trimellitic acid, hydroxyheptadecanoic acid, hydroxyoctadecanoic acid, hydroxyeicosanoic acid, hydroxydocosanoic acid, hydroxyhexacosanoic acid and hydroxytriacontanoic acid; Glyceguchi Ichinole, Trimethylo Norepropane, Pentaerythritonole, Diglyceronole, Triglycerono Les, dipentaerythritol, ethylene glycol, stearyl alcohol, 1, 6, 7-trich Droxyl 2, 2 Di (hydroxymethyl) 4-oxoheptane, sorbitan, sorbitol, polyoxyethylene sorbitan, polyoxyethylene sorbitol, ethylene glycol, polyethylene glycol, propylene glycol, polyethylene glycol, 2-methylol 1, 6, 7 Trihydroxy-2 Hydroxymethinore 4 1-year-old xoheptane, 1, 5, 6 trihydroxy-3-oxohexane, hexadenol, heptadecanol, octadecanol, decyltetradecanol, hexacosanol, triacontanol, 1,2—hexadecanediol, 2,3 heptadecanediol, 1,3—octadecanediol, 1,2 decyltetradecanediol and other alcohol-based mold release agents;

[0058] Glycerol stearate, butyl stearate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate, 12-hydroxystearic acid triglyceride, 12-hydroxy stearyl alcohol An aliphatic ester release agent that is a condensate of the above fatty acid and an alcohol compound, such as pentaerythritol-tetra-12-hydroxystearate, ethylene glycol-di-12-hydroxystearate, propylene glycolouse 12-hydroxystearate; Stearic acid amide, n-oleyl stearic acid amide, n-stearyl stearic acid amide, ethylene bis stearic acid amide, ethylene bis A fatty acid amide release agent which is a condensate of the above fatty acid with ammonium ethylenediamine, such as inamide, hexanemethylenebisbehenate amide, N-stearinole stearate amide, N-oleyl stearate amide; Examples include stearic acid power, such as lucum, a fatty acid metal litholytic release agent that is a metal salt of a metal and the above fatty acid; a silicone release agent.

[0059] Among them, ethylene bisstearic acid amide, which is preferred for fatty acid amide-based mold release agents, is preferred in that mold contamination due to bleed-out due to a small blending amount is suppressed, and white turbidity of the molded product is suppressed. Xamethylene bisbehenate amide is particularly preferred.

[0060] The amount of the release agent is not particularly limited as long as it does not impair the effects of the invention, but it is in the range of 0.01 to 5 weight percent with respect to 100 weight percent of the polymer (A). Preferably, it is more preferably in the range of 0.03 to 3 parts by weight, and particularly preferably in the range of 0.05 to 2 parts by weight. Mold release agent ratio S In this range, mold release is improved and mold contamination due to bleed-out is suppressed. This is preferable since the cloudiness of the molded body is further suppressed.

[0061] As a method for producing the resin composition of the present invention, a polymer (A), a hydride (B) or a polymer (B), an additive to be added if necessary, and the like are kneaded. A method of obtaining a pellet-shaped polymer composition by mixing the polymer (A), the hydride (B) or the polymer (B), and an additive to be added as necessary, in an appropriate solvent, And a method of obtaining a polymer composition by removing the solvent.

[0062] For the kneading, a melt kneader such as a single screw extruder, a twin screw extruder, a Banbury mixer, a kneader, a feeder loader, or the like can be used. The kneading temperature is preferably in the range of 200 to 350 ° C, more preferably in the range of 240 to 300 ° C. It is preferable that the kneading temperature is within this range because generation of thermal decomposition products of the polymer composition can be prevented. Also, when kneading, even if the components are added together and kneaded, they may be kneaded while adding in several portions.

[0063] The resin composition of the present invention is remarkably excellent in transparency and high-temperature and high-humidity resistance, so that it can be formed into various molded products.

[0064] (Molded product)

The molded product of the present invention is obtained by using the above-mentioned resin composition with a known thermoplastic resin molding method, for example, an injection molding method, an extrusion molding method, a cast molding method, an inflation molding method, a blow molding method, a vacuum molding method. It can be obtained by molding by press molding, compression molding, rotational molding, calendar molding, rolling molding, cutting molding or the like. Of these, the injection molding method or the press molding method is particularly preferred because it is excellent in dimensional accuracy and is capable of molding an aspherical shape.

[0065] (Application)

The resin composition of the present invention has the low hygroscopicity, chemical resistance, heat resistance, and low birefringence that the conventional resin composition has. Therefore, the resin composition of the present invention is useful in a wide range of fields as a molding material for various molded products. For example, optical materials such as optical disks, optical lenses, prisms, light diffusion plates, optical cards, optical fibers, optical mirrors, liquid crystal display element substrates, light guide plates, polarizing films, retardation films, etc .; liquids, powders, or solid chemicals Containers (liquid chemical containers for injection, ampoules, vials, prefilled syringes, infusion bags, sealed (Medicine bags, press 'through' packages, solid drug containers, eye drops containers, etc.), sampling containers (sampling test tubes for blood tests, caps for drug containers, blood collection tubes, sample containers, etc.), medical instruments (syringes, etc.), medical Sterilization containers such as instruments (for scalpels, forceps, gauze, contact lenses, etc.), experimental / analytical instruments (beakers, petri dishes, flasks, test tubes, centrifuge tubes, etc.), medical optical components (plastic lenses for medical examinations) Etc.), piping materials (medical infusion tubes, piping, fittings, valves, etc.), artificial organs and their components (tooth base, artificial heart, artificial tooth roots, etc.); treatment or transfer containers ( Tank, tray, carrier, case, etc.), protective material (carrier tape, separation film, etc.), piping (pipe, tube, valve, flow meter, filter, pump, etc.),

[0066] Electronic parts processing equipment for liquid containers (sampling containers, bottles, ampoules bags, etc.); coating materials (for electric wires, cables, etc.), consumer / industrial electronic equipment (copiers, combi Electrical insulation materials such as Uters, printers, TVs, VCRs, video cameras, etc.), structural members (parabolic antenna structural members, flat antenna structural members, radar dome structural members, etc.); general circuit boards (hard printed boards, flexible printed boards) Circuit boards such as high-frequency circuit boards (satellite communication equipment circuit boards, etc.); base materials for transparent conductive films (liquid crystal boards, optical memories, surface heating elements, etc.); semiconductor encapsulants (Transistor sealing material, IC sealing material, LSI sealing material, LED sealing material, etc.), electrical / electronic component sealing material (motor sealing material, capacitor sealing material, switch sealing material, Sensor Sealing material of the sealing material, etc.); automobile interior materials such as room cover of the mirror and the meter like; door mirror, a fender mirror, beam lens, light 'covers such exterior materials for automobiles; and the like. Among them, the molded body obtained by molding the resin composition of the present invention is excellent in transparency and resistance to high temperature and high humidity, and thus is suitable for a lens.

Example

[0067] The present invention will be described in more detail with reference to reference examples, examples and comparative examples, but the present invention is not limited to the following examples. Parts and percentages are by weight unless otherwise specified. Various physical properties were measured according to the following methods.

(Refractive index)

It was measured at 25 ° C. according to JIS K 0062 5. Measurement method for individual samples. [Polymerization conversion]

The reaction solution was measured by gas chromatography and calculated by quantifying unreacted monomers.

[Hydrogenation rate]

Calculated by ¹ H-NMR.

[Percentage of repeating units derived from 1, 2- and 3, 4-addition polymerization]

It was calculated by the Morero method using an infrared analysis method.

(Transparency test)

Using the molded body, the light transmittance at 700 nm with an optical path length of 65 mm was measured with ASA-300A manufactured by Nippon Denshoku Industries Co., Ltd., and the difference in light transmittance with the test piece obtained in Comparative Example 1 was determined. It was. It shows that transparency is so high that a value is small.

[0068] High temperature and high humidity resistance test

Using the molded body, the light transmittance at 700 nm with an optical path length of 65 mm was measured with ASA-300A manufactured by Nippon Denshoku Industries Co., Ltd., and then the molded body was placed in a high-temperature and high-humidity tester at 60 ° C, 95% relative Hold in a humidity environment for 120 hours, take it out rapidly to the room temperature environment (outside the tester) and place it in the room temperature for 24 hours, then measure the light transmittance, and from the light transmittance after the high temperature and high humidity test to the high temperature The value obtained by subtracting the light transmittance before the high humidity test was defined as the amount of decrease in the light transmittance before and after the high temperature and high humidity test. The smaller the decrease in light transmittance before and after the high-temperature and high-humidity test, the better the high-temperature and high-humidity resistance. In addition, the compact after the high-temperature and high-humidity test was observed with an optical microscope to confirm whether microcrazing had occurred.

[0069] [Polymer production example]

A nitrogen-substituted stainless steel pressure vessel was charged with 76.8 parts of styrene and 3.2 parts of isoprene, mixed and stirred to prepare a mixed monomer. Next, 320 parts of dehydrated cyclohexane, 4 parts of mixed monomer, and 0.1 part of dibutyl ether were charged into a stainless steel autoclave equipped with a nitrogen-substituted magnetic stirrer and stirred at 50 ° C for n-butyllithium. Hexane solution (concentration 15%) 0.445 parts of polymerization was added to initiate polymerization, and polymerization was carried out. After 0.5 hours from the start of polymerization (the polymerization conversion rate at this point was about 96%), 76 parts of the mixed monomer was continuously added over 1 hour. Completion of mixed monomer addition (at this point The polymerization conversion rate was about 95%.) After 0.5 hour, 0.1 part of isopropyl alcohol was added to stop the reaction, and a polymerization reaction solution in which the styrene-isoprene random copolymer was dissolved was obtained. It was.

[0070] Next, 3 parts of a stable nickel hydrogenation catalyst E22U (manufactured by JGC Corporation; 60% nickel-supported silica-alumina carrier) was added to and mixed with 400 parts of the above polymerization reaction solution, and the mixture was mixed. Then, put it into a stainless steel autoclave equipped with an electric heating device and an electromagnetic stirring device.

Hydrogen gas was supplied to the autoclave, and a hydrogenation reaction was carried out for 6 hours while maintaining the inside of the autoclave at 160 ° C. and 4.5 MPa while stirring. After completion of the hydrogenation reaction, pressure filtration was performed at a pressure of 0.25 MPa using a pressure filter equipped with Radiolite # 800 as a filter bed (manufactured by Ishizuchi 11 Shima Harima Heavy Industries Co., Ltd.). A colorless and transparent solution containing a cyclic hydrocarbon polymer was obtained. The ratio of the number of carbon-carbon double bonds after hydrogenation to the total number of carbon-carbon bonds (including aromatic rings) in the copolymer before hydrogenation was 0.02% or less. Tg is 126.5. C, Refractive index was 1.5070.

[0071] [Example 1]

The hydrogenated aromatic vinyl-conjugated gen block copolymer (E1) with 100 parts of the bull alicyclic hydrocarbon polymer obtained in the polymer production example modified with a hydroxyl group at the end of the main chain shown in Table 1. ) 0.3 parts, and tetrakis [methylene 3- (3 ', 5,1-di--butyl-4, monohydroxyphenol) propionate] methane (tinoc'speciality') as an antioxidant Chemicals Co., Ltd. Irganox 1010) 0.1 part, 12-hydroxystearic acid triglyceride 1.0 part as a release agent was added respectively, and a twin-screw kneader (Toshiba Machine Co., Ltd., TE M-35B, screw diameter 37 mm, L / D = 32, screw rotation speed 150 rpm, resin temperature 2 40 ° C., feed rate 10 kg), and extruded into a strand. This was cooled with water, cut with a pelletizer, and baked into pellets.

[0072] The obtained pellets were dried at 100 ° C for 4 hours using a hot air dryer in which nitrogen was circulated, and then the cylinder temperature was 240 ° C with an injection molding machine (FANUC, AUTOSHOT MODEL 30A). A molded body 1 having a length of 65 mm, a width of 65 mm, and a thickness of 3 mm was obtained at C, a mold temperature of 115 ° C, a primary injection pressure of 98. lMPa, and a secondary injection pressure of 78.4 MPa. Obtained compact 1 Were used to conduct a transparency test and a high temperature and high humidity resistance test. The results are shown in Table 2.

[0073] [Example 2]

Except using the hydride (E2) of the aromatic bu-conjugated conjugated block copolymer shown in Table 1, a molded product 2 was obtained in the same manner as in Example 1 to obtain a transparency test and a high temperature and high humidity resistance test. Went. The results are shown in Table 2.

[0074] [Example 3]

Except using the hydride (E3) of the aromatic bu-conjugated conjugated block copolymer shown in Table 1, a molded product 3 was obtained in the same manner as in Example 1 to obtain a transparency test and a high temperature and high humidity resistance test. Went. The results are shown in Table 2.

[0075] [Example 4]

Except for using the hydrogenated aromatic bulene conjugated block copolymer shown in Table 1 (E4), a molded product 4 was obtained in the same manner as in Example 1 to obtain a transparency test and a high temperature and high humidity resistance test. Went. The results are shown in Table 2.

[0076] [Comparative Example 1]

Except for not using a hydride of an aromatic vinyl-conjugated gen block copolymer in which the end of the main chain was modified with a hydroxyl group, a molded product 5 was obtained in the same manner as in Example 1 and evaluated for transparency. Using the obtained molded body 5, the light transmittance at 700 nm with an optical path length of 65 mm was measured with ASA-300A manufactured by Nippon Denshoku Industries Co., Ltd., and the light transmittance was 88.8%. Further, using the obtained molded body 5, a high temperature and high humidity resistance test was conducted. The results are shown in Table 2.

[0077] [Comparative Example 2]

Except using the hydride (E5) of the aromatic bu-conjugated conjugated block copolymer shown in Table 1, a molded product 6 was obtained in the same manner as in Example 1 to obtain a transparency test and a high temperature and high humidity resistance test. Went. The results are shown in Table 2.

[0078] [Comparative Example 3]

Except using the hydride (E6) of the aromatic bu-conjugated conjugated block copolymer shown in Table 1, a molded product 7 was obtained in the same manner as in Example 1 to obtain a transparency test and a high temperature and high humidity resistance test. Went. The results are shown in Table 2. [0079] [Table 1]

[0080] [Table 2] Table 2

* 1: Difference from the light transmittance of Comparative Example 1 at a wavelength of 700 nm

[0081] Table 2 shows the following.

The resin composition of the present invention, that is, comprising a vinyl alicyclic hydrocarbon polymer (A) and a hydride (B) of an aromatic vinyl conjugated gen block copolymer (b),

The aromatic vinyl-conjugated gen block copolymer (b) before hydrogenation is

2) The polymer block (ii) has 40% by weight or more of 1,2-addition polymerization and 3,4-addition polymerization repeating units in the repeating units derived from the conjugation compound constituting the polymer block (ii). And

3) A molded product obtained by molding a resin composition, which has a hydroxyl group at the end of the main chain, Excellent transparency and high temperature and humidity resistance (Examples 1 to 4).

[0082] On the other hand, a molded article formed only from the vinyl alicyclic hydrocarbon polymer (A) is excellent in transparency but extremely inferior in high temperature and high humidity (Comparative Example 1). In addition, a molded product obtained by molding a resin composition using a hydride (E5) of an aromatic vinyl-conjugated gen block copolymer that has not been modified with a hydroxyl group is excellent in transparency but is resistant to high temperatures and high temperatures. Poor wetness (Comparative Example 2). Further, in the repeating unit derived from the conjugated genie block (Π), the ratio of repeating units derived from 1,2- and 3,4-addition polymerization is not more than 0% by weight. A molded product formed from a resin composition using a hydride (E6) of an aromatic vinyl-conjugated gen block copolymer is excellent in high temperature and high humidity resistance but inferior in transparency (Comparative Example 3). Recognize.

Industrial applicability

The resin composition of the present invention is suitable as an optical molding material because it is excellent in transparency and high temperature and high humidity resistance.

Claims

The scope of the claims

[1] It contains a bullyalicyclic hydrocarbon polymer (A) and a hydride (B) of an aromatic vinyl-conjugated gen block copolymer (b),

The aromatic vinyl-conjugated gen block copolymer (b) before hydrogenation is

2) The polymer block (ii) has 40% by weight or more of the repeating units derived from the conjugation compound that constitutes the repeating unit that are subjected to 1, 2 addition polymerization and 3, 4 addition polymerization, and

3) It has a hydroxyl group at the end of the main chain,

A rosin composition characterized by that.

[2] The resin composition according to claim 1, wherein the polymer (A) has 50% by weight or more of a repeating unit derived from a vinyl alicyclic hydrocarbon compound.

[3] Polymer (A) is a polymer in which 80 mol% or more of all carbon-carbon unsaturated bonds including aromatic rings in polymer (a) having a repeating unit derived from an aromatic vinyl compound are hydrogenated. The rosin composition according to claim 1.

[4] The resin composition according to claim 1, wherein the polymer (A) has a glass transition temperature of 80 to 250 ° C.

[5] The resin composition according to claim 1, wherein the polymer (A) has a weight average molecular weight of 10,000 to 500,000 and a molecular weight distribution (= weight average molecular weight Z number average molecular weight) of 5 or less.

[6] The resin composition according to claim 1, wherein the block copolymer (b) has 50 mol% or more of hydroxyl groups at the ends of the main chain.

[7] Block copolymer (b) is polymer block (i) Polymer block (ii) Polymer block (i

The rosin composition according to claim 1, wherein

[8] The ratio of the polymer block (i) in the block copolymer (b) is 15 to 55% by weight.

The rosin composition according to 1.

[9] In the hydride (B), less than 40 mol% of the aromatic ring in the polymer block (i) of the block copolymer (b) is hydrogenated, and the carbon-carbon double in the polymer block (ii) 2. The resin composition according to claim 1, wherein 60 mol% or more of the bonds are hydrogenated.

10. The resin composition according to claim 1, wherein the hydride (B) has a glass transition temperature of 30 ° C or lower.

[11] The resin composition according to claim 1, wherein the hydride (B) is 0.001 to 50 parts by weight relative to 100 parts by weight of the polymer (A).

[12] The absolute value of the difference between the refractive index n (A) of the polymer (A) and the refractive index n (B) of the hydride (B) is 0

D D

The rosin composition according to claim 1, which is 01 or less.

[13] A molded article obtained by molding the resin composition according to claim 1.

14. The molded article according to claim 13, which is a lens.