JP4985397B2 - Resin composition and molded body - Google Patents

Description

  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 high-humidity resistance and a molded body formed by molding the resin composition.

  Vinyl alicyclic hydrocarbon polymers are excellent in transparency, low moisture absorption, chemical resistance, heat resistance, and low birefringence, and are used in optical members such as lenses and optical disk substrates. However, a molded body composed solely of a vinyl alicyclic hydrocarbon polymer may become cloudy (inferior in high temperature and high humidity resistance) when placed at room temperature suddenly after being placed in a high temperature and high humidity environment for a long time. is there. Thus, attempts have been made to improve high temperature and high humidity resistance by adding a compounding agent to the vinyl alicyclic hydrocarbon polymer. For example, Patent Document 1 and Patent Document 2 disclose a resin composition in which a soft polymer such as a styrene-butadiene-styrene block copolymer is blended with a vinyl alicyclic hydrocarbon polymer, and the resin composition is molded. Thus, it has been disclosed that a small lens such as a pickup lens having transparency and high temperature and high humidity resistance at practical levels can be obtained.

JP 2002-148401 A US Pat. No. 6,965,003

Resin lenses are easy to process and lightweight, so it is considered to apply resin lenses not only to small lenses such as pickup lenses, but also to large image lenses such as projector lenses and camera lenses. ing. The image lens is required to be a large lens having no transparency and excellent transparency.
However, when a large image lens is molded with a resin composition containing a vinyl alicyclic hydrocarbon polymer and a soft polymer described in Patent Documents 1 and 2, the lens may be slightly clouded. The inventor investigated the cause of the cloudiness of the lens, and the resin composition described in Patent Document 1 and the like has a high temperature and high humidity resistance at a practical level, but has insufficient transparency for a large lens. I understood.
An object of the present invention is to provide a resin composition that is more excellent in transparency and high temperature and humidity resistance and a molded body using the same, in view of the above situation.

  In order to achieve the above object, the present inventor has intensively studied a soft polymer to be blended with the vinyl alicyclic hydrocarbon polymer (A). As a result, the main chain has a hydroxyl group at the end and a conjugated diene compound. Hydrogenated aromatic vinyl-conjugated diene block copolymer (b) having a repeating unit obtained by 1,2-addition polymerization or 3,4-addition polymerization at a specified ratio (B) It has been found that by using as a soft polymer, a large lens can be obtained which is remarkably excellent in transparency and which does not cause white turbidity even after being left at high temperature and high humidity and then returned to room temperature. The present inventor has further studied based on these findings and has completed the present invention.

Thus, the present invention comprises a vinyl alicyclic hydrocarbon polymer (A) and a hydride (B) of an aromatic vinyl-conjugated diene block copolymer (b),
The aromatic vinyl-conjugated diene block copolymer (b) before hydrogenation is
1) It consists of a polymer block (i) composed of a repeating unit derived from an aromatic vinyl compound and a polymer block (ii) composed of a repeating unit derived from a conjugated diene compound,
2) The polymer block (ii) has 40% by weight or more of repeating units obtained by 1,2-addition polymerization and 3,4-addition polymerization in the repeating units derived from the conjugated diene compound constituting the polymer block (ii), And 3) having a hydroxyl group at the end of the main chain,
It is a resin composition characterized by this.
Moreover, this invention is a molded object formed by shape | molding this resin composition.

The resin composition of the present invention is remarkably excellent in transparency and high temperature and high humidity resistance. A large lens obtained by molding this resin composition has no haze.
Although the reason why a large lens without cloudiness can be obtained by the resin composition of the present invention is not clear, it is more than a certain amount in the molecular chain of the polymer block (II) in the polymer (B) or hydride (B). The branched structure (repeating unit formed by 1,2-addition polymerization or 3,4-addition polymerization of a conjugated diene compound) reduces the cohesive energy density, and the polymer (B) or The hydride (B) can be uniformly dispersed, and a domain having a very small size can be formed. 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 aggregation of moisture that has been absorbed, and suppresses the generation of microcraze. Therefore, after leaving the lens under high temperature and high humidity, It is thought that white turbidity does not occur even if it returns.

The resin composition of the present invention comprises a vinyl alicyclic hydrocarbon polymer (A) and a hydride (B) of an aromatic vinyl-conjugated diene block copolymer (b),
The aromatic vinyl-conjugated diene block copolymer (b) before hydrogenation is
1) It consists of a polymer block (i) composed of a repeating unit derived from an aromatic vinyl compound and a polymer block (ii) composed of a repeating unit derived from a conjugated diene compound,
2) The polymer block (ii) has 40% by weight or more of repeating units obtained by 1,2-addition polymerization and 3,4-addition polymerization in the repeating units derived from the conjugated diene compound constituting the polymer block (ii), And 3) having a hydroxyl group at the end of the main chain.

(Vinyl alicyclic hydrocarbon polymer (A))
The vinyl alicyclic hydrocarbon polymer (A) used in the present invention has a repeating unit obtained by vinyl addition polymerization of a vinyl alicyclic hydrocarbon compound, that is, a repeating unit having an alicyclic structure in the side chain. It is a polymer. 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. In addition, since the repeating unit derived from the vinyl alicyclic hydrocarbon compound has the same structure as the repeating unit obtained by vinyl addition polymerization of the vinyl alicyclic hydrocarbon compound, vinyl addition polymerization of the aromatic vinyl compound, It is then assumed to contain repeat units obtained by hydrogenating the aromatic ring.

  The number of carbon atoms constituting the alicyclic structure is usually in the range of 4 to 30, preferably 5 to 20, more preferably 5 to 15, and most preferably 6. When the number of carbon atoms constituting the alicyclic structure is in this range, the heat resistance and molding processability of the resulting resin composition and the mechanical strength of the resulting molded article are excellent.

The glass transition temperature (Tg) of the polymer (A) used in the present invention is preferably in the range of 80 to 250 ° C, more preferably 90 to 200 ° C, and particularly preferably 100 to 150 ° C. 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 balance between the strength characteristics and heat resistance of the resulting molded article and the molding processability of the resulting resin composition is excellent.
In the present invention, the glass transition temperature (Tg) is a value measured under the condition of 10 ° C./min using a differential scanning calorimeter.

  The weight average molecular weight (Mw) of the polymer (A) is preferably in the range of 10,000 to 500,000, more preferably 30,000 to 350,000, and still more preferably 50,000 to 200,000. If Mw is too small, the strength characteristics of the resulting molded article are poor, and if it is too large, the moldability of the resulting resin composition is poor, and the birefringence of the resulting 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).

  The molecular weight distribution (Mw / Mn) 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. When this Mw / Mn is too large, the mechanical properties and heat resistance of the obtained molded product are lowered. In particular, Mw / Mn is more preferably 2 or less, more preferably 1.7 or less, in order to highly balance the mechanical strength, heat resistance, and moldability of the resulting resin composition. Most preferred is 1.5 or less. 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.

  In order to make Mw / Mn of a polymer (A) into the said preferable range, living polymerization methods, such as living anion polymerization, are preferable among the said polymerization methods. For example, living anionic polymerization is carried out in the temperature range of usually 0 ° C. to 150 ° C., preferably 10 ° C. to 100 ° C., particularly preferably 20 ° C. to 80 ° C. in the presence of a polymerization initiator. Examples of the initiator include monoorganolithium such as n-butyllithium, sec-butyllithium, t-butyllithium, hexyllithium, and phenyllithium, dilithiomethane, 1,4-dilithiobutane, 1,4-dilithio-2-ethylcyclohexane, and the like. Examples include polyfunctional organolithium compounds.

  Examples of such a polymer (A) include an addition polymer of a saturated alicyclic vinyl compound, an addition polymer of an unsaturated alicyclic vinyl compound and a hydride thereof, and an aromatic ring hydrogen of an addition polymer of an aromatic vinyl compound. And the like.

  Examples of the saturated alicyclic vinyl compound include vinylcyclohexane, 3-methylisopropenylcyclohexane, and those having a substituent such as a halogen group, an alkoxy group, and a hydroxyl group.

  Examples of unsaturated alicyclic vinyl compounds include 4-vinylcyclohexene, 4-isopropenylcyclohexene, 1-methyl-4-vinylcyclohexene, 2-methyl-4-vinylcyclohexene, 1-methyl-4-isopropenylcyclohexene, 2 -Methyl-4-isopropenylcyclohexene, and those having a substituent such as a halogen group, an alkoxy group, and a hydroxyl group.

  Examples of the aromatic vinyl compound include styrene, α-methylstyrene, α-ethylstyrene, α-propylstyrene, α-isopropylstyrene, α-t-butylstyrene, 2-methylstyrene, 3-methylstyrene, and 4-methylstyrene. 2,4-diisopropylstyrene, 2,4-dimethylstyrene, 4-t-butylstyrene, 5-t-butyl-2-methylstyrene, 4-monochlorostyrene, dichlorostyrene, 4-monofluorostyrene, 4-phenyl Examples thereof include styrene and those having a substituent such as a halogen group, an alkoxy group, or a hydroxyl group.

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

  The polymer (A) used in the present invention is a repeat derived from 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 unit. Examples of the copolymerizable monomer include linear vinyl compounds and linear conjugated diene compounds. The linear vinyl compound and the linear conjugated diene compound may be those in which a linear chain is branched.

  Examples of the linear vinyl compound include chain olefins such as ethylene, propylene, 1-butene, 1-pentene, and 4-methyl-1-pentene. Among these, ethylene, propylene, and 1-butene are most preferable.

  Examples of the linear conjugated diene compound include 1,3-butadiene, 1,2-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, and 1,3-hexadiene. It is done. Of these linear vinyl compounds and linear conjugated dienes, linear conjugated diene compounds are preferred, and 1,3-butadiene and isoprene are particularly preferred. These linear vinyl compounds and linear conjugated dienes can be used alone or in combination of two or more.

  The polymer (A) is a known polymerization method such as radical polymerization, anion polymerization, cation polymerization, living anion polymerization, living cation polymerization, coordination anion polymerization, coordination cation polymerization, or living radical polymerization. Can be obtained by homopolymerization or copolymerization with hydrogenation and hydrogenation as necessary.

  A polymer (A) is not restrict | limited by the form of copolymerization, Any of a random copolymer, a pseudorandom copolymer, a block copolymer, a gradient block copolymer, etc. may be sufficient. The polymer (A) obtained by block copolymerization is not limited by the number of blocks, and examples thereof include a diblock structure, a triblock structure, a tetrablock structure, a pentablock structure, a hexablock structure, and a heptablock structure. It is done. Moreover, the block length of each block may be the same or different.

  The polymer (A) obtained through addition polymerization of an aromatic vinyl compound generally has a hydrogenation rate of all carbon-carbon unsaturated bonds including an aromatic ring of 80 mol% or more, preferably 95 mol% or more. More preferably, it is 99-100 mol%. That is, in the polymer (A) obtained through addition polymerization and hydrogenation of an aromatic vinyl 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.

  The steric configuration of the polymer (A) used in the present invention may be any of atactic, isotactic, and syndiotactic. For example, any one of 0 to 100% in syndiotacticity by dyad display Can also be used.

For the polymerization, methods such as solution polymerization and slurry polymerization can be used. In consideration of removal of reaction heat, solution polymerization is preferable. In solution polymerization, an inert solvent capable of dissolving the polymer and its hydride is used. Examples of the inert solvent include aliphatic hydrocarbons such as n-butane, n-pentane, isopentane, n-hexane, n-heptane, and isooctane; cyclopentane, cyclohexane, methylcyclopentane, methylcyclohexane, decalin, bicyclo [4 .3.0] nonane, tricyclo [4.3.0.1 ^2,5 ] decane and other alicyclic hydrocarbons; aromatic hydrocarbons such as benzene and toluene, among others, alicyclic carbonization Use of hydrogen is preferable because it can be used as it is 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 the monomers used.

(Aromatic vinyl-conjugated diene block copolymer (b) hydride (B))
The hydride (B) of the aromatic vinyl-conjugated diene block copolymer (b) used in the present invention is obtained by hydrogenating the aromatic vinyl-conjugated diene block copolymer (b). Of the aromatic vinyl-conjugated diene block copolymer (b)
1) It consists of a polymer block (i) composed of a repeating unit derived from an aromatic vinyl compound and a polymer block (ii) composed of a repeating unit derived from a conjugated diene compound,
2) The polymer block (ii) has 40% by weight or more of repeating units obtained by 1,2-addition polymerization and 3,4-addition polymerization in the repeating units derived from the conjugated diene compound constituting the polymer block (ii), And 3) having a hydroxyl group at the end of the main chain.

Examples of the aromatic vinyl compound constituting the polymer block (i) of the copolymer (b) include styrene, α-methylstyrene, 1-vinylnaphthalene, p-methylstyrene, 4-propylstyrene, t-butylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4- (phenylbutyl) styrene, divinylbenzene, N, N-dimethyl-p-aminoethylstyrene, N, N-diethyl-p- Examples include aminoethyl styrene and vinyl pyridine. Among these, styrene and α-methylstyrene are preferable, and styrene is more preferable.
These aromatic vinyl compounds may be used alone or in combination of two or more.
When two or more aromatic vinyl compounds are used in combination, the polymer block (i) comprising repeating units derived from the aromatic vinyl compound may be a random copolymer of two or more aromatic vinyl compounds. Further, it may be a block copolymer or a tapered copolymer.

  Examples of the conjugated diene compound constituting the polymer block (ii) of the copolymer (b) include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2- Examples include methyl-1,3-pentadiene, 1,3-hexadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, chloroprene, and the like. Among these, 1,3-butadiene, isoprene and 1,3-pentadiene are preferable, 1,3-butadiene and isoprene are more preferable, and isoprene is particularly preferable.

These conjugated diene compounds are used alone or in combination of two or more.
When two or more kinds of conjugated diene compounds are used in combination, the polymer block (ii) composed of repeating units derived from the conjugated diene compound may be obtained by random copolymerization of two or more kinds of conjugated diene compounds. It may be polymerized or tapered copolymerized.

The combination of the conjugated diene compound is not particularly limited, but a combination of isoprene and 1,3-butadiene is preferable.
When the combination of the conjugated diene compound is isoprene and 1,3-butadiene, the proportion of repeating units derived from isoprene in all repeating units of the conjugated diene block (ii) is preferably 60% or more.

The mode of the block of the aromatic vinyl-conjugated diene block copolymer (b) is not particularly limited, and examples thereof include a diblock, a triblock, and more multiblocks. Specifically, the polymer block (i) and the polymer block (ii) are ((i)-(ii)) _n , (ii)-((i)-(ii)) _n , ((i) -(Ii)) The block aspect shown by _n- (i) is mentioned. Here, n is an integer of 1 or more. Among these, the aromatic vinyl-conjugated diene block copolymer (b) having a block form represented by (i)-(ii)-(i) is preferable.

  The proportion 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.

The polymer block (ii) has 40% by weight or more of the repeating units derived from the conjugated diene compound constituting the repeating unit which are subjected to 1,2-addition polymerization and 3,4-addition polymerization. . By having 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 when the conjugated diene compound is subjected to addition polymerization, a repeating unit derived from 1,2-addition polymerization, a repeating unit derived from 3,4-addition polymerization, and a repeating unit derived from 1,4-addition polymerization One of these is formed. For example, when 2-methyl-1,3-pentadiene is used as the conjugated diene compound, a repeating unit represented by (1-methyl-1- (1-propylene)) ethylene is formed by 1,2-addition polymerization. The repeating unit represented by 1-isopropenyl-2-methylethylene is formed by 3,4-addition polymerization, and the repeating unit represented by 1,3-dimethyl-2-butenylene is formed by 1,4-addition polymerization. It is formed. The ratio of 1,2-addition polymerization and 3,4-addition polymerization repeating units in the repeating unit derived from the conjugated diene compound in the polymer block (ii) is calculated by the Morero method using infrared analysis. be able to.

  The polymer (b) has a hydroxyl group at the end of the main chain. The polymer (b) only needs to contain 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 main chain end. If it is.

The aromatic vinyl-conjugated diene block copolymer (b) used in the present invention can be obtained by applying an ionic polymerization method such as anionic polymerization or cationic polymerization, a single site polymerization method, a radical polymerization method, or the like. It is obtained by forming a skeleton (main chain) and then modifying the end of the main chain to a hydroxyl group.
For example, a desired molecular structure and molecular weight can be obtained by a sequential polymerization method in which an aromatic vinyl compound is polymerized in an inert organic solvent such as n-hexane or cyclohexane using an organolithium compound as an initiator, and then a conjugated diene compound is polymerized. Next, a compound having an oxirane skeleton such as ethylene oxide, propylene oxide and styrene oxide is added, and then an active hydrogen-containing compound such as alcohols, carboxylic acids and water is added to perform polymerization. It can be obtained by stopping.

  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.

Examples of the organic lithium compound include monolithium compounds such as methyllithium, ethyllithium, pentyllithium, and butyllithium; dilithium compounds such as naphthalenedilithium and dilithiohexylbenzene.
The proportion of the organolithium compound used is not particularly limited, but is usually 0.005 to 0.2 parts by weight with respect to 100 parts by weight of the monomer.

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.

  Although the reaction temperature of a polymerization reaction is not specifically limited, Usually, it is 0-80 degreeC. Moreover, although the reaction time of a polymerization reaction is not specifically limited, Usually, it is 0.5 to 50 hours.

The ratio of the repeating unit derived from 1,2- and 3,4-addition polymerization in the repeating unit derived from the conjugated diene compound in the conjugated diene block (ii) is the same as that in the polymerization of the conjugated diene compound. It can be adjusted by using it as a catalyst.
Examples of Lewis bases include ethers such as dimethyl ether, diethyl 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′-tetramethylethylenediamine (TMEDA) , Amine compounds such as pyridine, tributylamine, N-methylmorpholine; and the like.
The amount of these Lewis bases used is usually in the range of 0.1 to 1000 mol with respect to 1 mol of lithium as a polymerization initiator.

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. For example, there is a method of bringing the polymer (b) and hydrogen into contact with each other 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.

Examples of hydrogenation catalysts include Raney nickel, heterogeneous catalysts such as those in which a metal such as Pt, Pd, Ru, Rh, Ni is supported on a carrier such as carbon, alumina, diatomaceous earth, or transition metals and alkylaluminum compounds or alkyls. Examples include Ziegler type catalysts composed of a combination with lithium or the like. Of these, Ziegler catalysts composed 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 room temperature to 250 ° C, more preferably 20 to 150 ° C. The reaction time is preferably 0.1 to 100 hours.

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 of the resulting molded body, the machine Excellent in mechanical strength, heat resistance, and weather resistance.

  As described above, the hydride (B) of the aromatic vinyl-conjugated diene block copolymer (b) is obtained. This hydride (B) is composed of a polymer block (I) having a repeating unit derived from an aromatic vinyl compound and a polymer block (II) having a hydrogenated repeating unit derived from a conjugated diene compound. The combined block (II) comprises 40 weights of 1,2-addition polymerization and 3,4-addition polymerization repeating units in the hydrogenated repeating unit derived from the conjugated diene compound constituting the block (II). % Or more, and a polymer (B) having a hydroxyl group at the end of the main chain.

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.
In addition, the polymer (B) suitable for use in the present invention preferably has a polymer block (I) ratio of 15 to 55% by weight, more preferably 20 to 50% by weight, particularly in the polymer (B). Preferably it is the range of 25 to 45 weight%.

The proportion of the hydrogenated repeating unit derived from the conjugated diene compound in the polymer block (II) is the sum of the non-hydrogenated repeating unit derived from the conjugated diene compound and the hydrogenated repeating unit derived from the conjugated diene compound. The amount is usually 60% or more, preferably 70% or more, more preferably 80% or more based on the amount.
Aromatic rings are hydrogenated in the polymer block (I) in which the aromatic vinyl compound-derived repeating units are usually less than 40%, preferably less than 30%, more preferably less than 10%, most preferably less than 5%. Repeating units may be included.

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

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

  Although the ratio of the polymer (A) and the hydride (B) or the polymer (B) in the resin composition of the present invention is not particularly limited, the hydride (B) with respect to 100 parts by weight of the polymer (A). Alternatively, the polymer (B) is preferably 0.001 to 50 parts by weight, more preferably 0.01 to 10 parts by weight, particularly preferably 0.05 to 5 parts by weight, and 0.2 to 0. .8 parts by weight is most preferred.

The resin composition of the present invention comprises the refractive index (n _D (A)) of the polymer (A) used and the refractive index (n _D (B)) of the hydride (B) or polymer (B) used. The difference (| n _D (A) −n _D (B) |) is preferably 0.01 or less, and (| n _D (A) −n _D (B) |) is 0.007 or less. More preferably, it is further more preferable in it being 0.004 or less. (| N _D (A) −n _D (B) |) is small that the difference between the refractive index of the polymer (A) used and the refractive index of the hydride (B) of the polymer used is small. means. When (| n _D (A) −n _D (B) |) is in this range, the transparency of the resin composition is more excellent.

  In the present invention, the refractive index is JIS K0062 5. It is a value measured at 25 ° C. according to the method for measuring an individual sample.

If necessary, other additives can be added to the resin composition of the present invention.
Other additives include, for example, stabilizers such as antioxidants, light stabilizers, heat stabilizers, ultraviolet absorbers, near infrared absorbers; resin modifiers such as mold release agents and plasticizers; dyes and pigments And coloring agents such as antistatic agents and light diffusing agents.

  Examples of the antioxidant include phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants and the like. These antioxidants can be used alone or in combination of two or more. Among these, phenolic antioxidants, particularly alkyl-substituted antioxidants can be suitably used. The addition amount of the antioxidant is preferably 0.01 to 2 parts by weight and more preferably 0.02 to 1 part by weight with respect to 100 parts by weight of the polymer (A).

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

  As the release agent, paraffins, naphthenes, aromatics, low molecular weight polyethylene wax, low molecular weight polypropylene wax, low molecular weight polystyrene wax or oxides thereof, modified products such as carboxylic acid, hydroxyl group, ester group, etc. 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, trimellitic acid, hydroxyheptadecanoic acid, Fatty acid release agents such as hydroxyoctadecanoic acid, hydroxyeicosanoic acid, hydroxydocosanoic acid, hydroxyhexacosanoic acid, hydroxytriacontanoic acid; glycerol, trimethylolpropane, pentaerythritol, diglycerol, triglycerol, dipentaeryth Tall, ethylene glycol, stearyl alcohol, 1,6,7-trihydroxy-2,2-di (hydroxymethyl) -4-oxoheptane, sorbitan, sorbitol, polyoxyethylene sorbitan, polyoxyethylene sorbitol, ethylene glycol, polyethylene Glycol, propylene glycol, polyethylene glycol, 2-methyl-1,6,7-trihydroxy-2-hydroxymethyl-4-oxoheptane, 1,5,6-trihydroxy-3-oxohexane, hexadecanol, hepta Decanol, octadecanol, decyltetradecanol, hexacosanol, triacontanol, 1,2-hexadecanediol, 2,3-heptadecanediol, 1,3-octadecanediol, 1,2-decyltetra Alcohol-based release agents such as Kanji ol;

  Glycerol stearate, butyl stearate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate, 12-hydroxystearic acid triglyceride, 12-hydroxystearic acid stearyl alcohol, pentaerythritol- An aliphatic ester release agent which is a condensate of the fatty acid and an alcohol compound, such as tetra-12-hydroxystearate, ethylene glycol-di-12-hydroxystearate, propylene glycol-di-12-hydroxystearate; Stearic acid amide, n-oleyl stearic acid amide, n-stearyl stearic acid amide, ethylene bis stearic acid amide, ethylene vinyl Oleic acid amide, hexanemethylene bisbehenic acid amide, N-stearyl stearic acid amide, N-oleyl stearic acid amide, and the like, fatty acid amide release agents that are condensates of the above fatty acids with ammonia, ethylenediamine, etc .; metals such as calcium stearate And fatty acid metal soap release agents that are metal salts of the above fatty acids and silicone release agents.

  Among them, the blending amount may be small, the mold stain due to bleed-out is suppressed, and the white turbidity of the molded product is suppressed, fatty acid amide type release agent is preferable, ethylene bis stearic acid amide, hexamethylene bis behenic acid Amide is particularly preferred.

  The amount of the release agent is not particularly limited as long as it does not impair the effects of the invention, but is preferably in the range of 0.01 to 5 parts by weight with respect to 100 parts by weight of the polymer (A). More preferably in the range of 0.03 to 3 parts by weight, particularly preferably in the range of 0.05 to 2 parts by weight. When the ratio of the release agent is within this range, it is preferable because release properties are improved, mold contamination due to bleeding out is suppressed, and white turbidity of the molded product is further suppressed.

  As a method for producing the resin composition of the present invention, a polymer (A), a hydride (B) or a polymer (B), and an additive to be added as necessary are kneaded to form a pellet. A method for obtaining a polymer composition of: a polymer (A), a hydride (B) or a polymer (B) in an appropriate solvent, an additive to be added if necessary, etc., and the solvent is removed. The method of obtaining a polymer composition by this; etc. are mentioned.

  For kneading, a melt kneader such as a single-screw extruder, a twin-screw extruder, a Banbury mixer, a kneader, or a feeder ruder 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. When the kneading temperature is within this range, it is preferable because generation of a thermal decomposition product of the polymer composition can be prevented. Further, when kneading, the components may be added together and kneaded, or may be kneaded while adding in several times.

  Since the resin composition of the present invention is remarkably excellent in transparency and high temperature and high humidity resistance, it can be formed into various molded products.

(Molded body)
The molded body of the present invention is obtained by molding the above resin composition into a known thermoplastic resin molding method, for example, injection molding method, extrusion molding method, cast molding method, inflation molding method, blow molding method, vacuum molding method, press molding. It can be obtained by molding by the method, compression molding method, rotational molding method, calendar molding method, rolling molding method, cutting molding method or the like. Among these, an injection molding method or a press molding method that is excellent in dimensional accuracy and can be molded into an aspherical shape is preferable, and an injection molding method is particularly preferable.

(Use)
The resin composition of the present invention has the low hygroscopicity, chemical resistance, heat resistance, and low birefringence that conventional resin compositions have. 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 .; containers for liquids, powders, or solid chemicals (Liquid chemical containers for injection, ampoules, vials, prefilled syringes, infusion bags, sealed medicine bags, press-through packages, solid chemical containers, eye drops containers, etc.), sampling containers (sampling test tubes for blood tests, chemical containers) Caps, blood collection tubes, specimen containers, etc.), medical instruments (syringes, etc.), sterilization containers such as medical instruments (for scalpels, forceps, gauze, contact lenses, etc.), experimental and 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, Tubes, fittings, valves, etc.), medical devices such as artificial organs and their components (tooth base, artificial heart, artificial tooth root, etc.); processing or transfer containers (tanks, trays, carriers, cases, etc.), protective materials (Carrier tape, separation film, etc.), piping (pipe, tube, valve, flow meter, filter, pump, etc.),

  Electronic parts processing equipment for liquid containers (sampling containers, bottles, ampoule bags, etc.); coating materials (for electric wires, cables, etc.), consumer / industrial electronic equipment (copiers, computers, printers, televisions) , Video decks, video cameras, etc.), electrical insulating materials such as structural members (parabolic antenna structural members, flat antenna structural members, radar dome structural members, etc.); general circuit boards (hard printed boards, flexible printed boards, multilayer printed wiring boards) Etc.), circuit boards such as high-frequency circuit boards (satellite communication equipment circuit boards, etc.); transparent conductive film (liquid crystal substrates, optical memories, surface heating elements, etc.) base materials; semiconductor sealing materials (transistor sealing materials, IC sealing material, LSI sealing material, LED sealing material, etc.), electrical / electronic component sealing material (motor sealing material, capacitor sealing material, switch Sealing materials, sensor sealing materials, etc .; automotive interior materials such as room mirrors and meter covers; automotive exterior materials such as door mirrors, fender mirrors, beam lenses, and light covers; . Among these, a molded article obtained by molding the resin composition of the present invention is excellent in transparency and high temperature and high humidity resistance, and is therefore suitable for a lens.

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% are based on weight unless otherwise specified. Various physical properties were measured according to the following methods.
[Refractive index]
JIS K 0062 5. According to the measurement method of an individual sample, it measured at 25 degreeC.
[Polymerization conversion]
The reaction solution was measured by gas chromatography and calculated by quantifying unreacted monomers.
[Hydrogenation rate]
Calculated by ¹ H-NMR.
[Ratio 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 shows that transparency is so high that a value is small.

[High temperature and 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 60 ° C. and 95% relative humidity in a high temperature and high humidity tester. Hold it in the environment for 120 hours, take it out rapidly to the room temperature environment (outside the tester), place it in the room temperature for 24 hours, measure the light transmittance, and determine the light transmittance from the high temperature and high humidity test from the high temperature and high humidity. The value obtained by subtracting the light transmittance before the 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. Further, the molded body after the high-temperature and high-humidity test was observed with an optical microscope, and it was confirmed whether microcraze was generated.

[Polymer production example]
To a stainless steel pressure vessel substituted with nitrogen, 76.8 parts of styrene and 3.2 parts of isoprene were added and 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 electromagnetic stirrer and stirred at 50 ° C. with a hexane solution of n-butyllithium ( Polymerization was started by adding 0.454 parts (concentration 15%) and polymerization was performed. After 0.5 hours had elapsed 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. 0.5 hours after the end of the addition of the mixed monomer (the polymerization conversion rate at this time was about 95%), 0.1 part of isopropyl alcohol was added to stop the reaction, and random copolymerization of styrene-isoprene A polymerization reaction solution in which the coalescence was dissolved was obtained.

Next, 3 parts of a stabilized nickel hydrogenation catalyst E22U (manufactured by JGC Chemical Co., Ltd .; 60% nickel-supported silica-alumina carrier) was added to and mixed with 400 parts of the above polymerization reaction solution to obtain a mixture, which was mixed with an electric heating device A stainless steel autoclave equipped with a magnetic stirrer was charged.
Hydrogen gas was supplied to the autoclave and a hydrogenation reaction was performed for 6 hours while maintaining the temperature inside the autoclave at 160 ° C. and 4.5 MPa while stirring. After completion of the hydrogenation reaction, pressure filtration at a pressure of 0.25 MPa using a pressure filter (Ishikawajima-Harima Heavy Industries, Ltd., Funda filter) equipped with Radiolite # 800 as a filter bed, vinyl alicyclic carbonization A colorless and transparent solution containing a hydrogen 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 was 126.5 ° C., and the refractive index was 1.5070.

[Example 1]
A hydride of an aromatic vinyl-conjugated diene block copolymer in which the end of the main chain shown in Table 1 is modified with a hydroxyl group with respect to 100 parts of the vinyl alicyclic hydrocarbon polymer obtained in the polymer production example ( E1) 0.3 parts, and tetrakis- [methylene-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate] methane as an antioxidant, manufactured by Ciba Specialty Chemicals Irganox 1010) 0.1 part and 12 parts of 12-hydroxystearic acid triglyceride as a release agent were added respectively, and a biaxial kneader (Toshiba Machine Co., Ltd., TEM-35B, screw diameter 37 mm, L / D = 32, screw rotation speed 150 rpm, resin temperature 240 ° C., feed rate 10 kg / hour) and extruded into a strand shape. This was cooled with water, cut with a pelletizer, and pelletized.

  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. and the mold temperature was 115 ° C. using an injection molding machine (manufactured by 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 a primary injection pressure of 98.1 MPa and a secondary injection pressure of 78.4 MPa. Using the obtained molded body 1, a transparency test and a high temperature and high humidity resistance test were conducted. The results are shown in Table 2.

[Example 2]
Except having used the hydride (E2) of the aromatic vinyl-conjugated diene block copolymer shown in Table 1, a molded product 2 was obtained in the same manner as in Example 1, and a transparency test and a high temperature and high humidity resistance test were obtained. Went. The results are shown in Table 2.

[Example 3]
Except having used the hydride (E3) of the aromatic vinyl-conjugated diene block copolymer shown in Table 1, a molded product 3 was obtained in the same manner as in Example 1, and a transparency test and a high temperature and high humidity resistance test were obtained. Went. The results are shown in Table 2.

[Example 4]
Except having used the hydride (E4) of the aromatic vinyl-conjugated diene block copolymer shown in Table 1, a molded body 4 was obtained in the same manner as in Example 1, and a transparency test and a high temperature and high humidity resistance test were obtained. Went. The results are shown in Table 2.

[Comparative Example 1]
Except not using the hydride of the aromatic vinyl-conjugated diene block copolymer in which the terminal 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 the transparency was evaluated. . When the light transmittance at 700 nm with an optical path length of 65 mm was measured using the obtained molded product 5 with ASA-300A manufactured by Nippon Denshoku Industries Co., Ltd., the light transmittance was 88.8%. In addition, a high temperature and high humidity resistance test was performed using the obtained molded body 5. The results are shown in Table 2.

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

[Comparative Example 3]
Except having used the hydride (E6) of the aromatic vinyl-conjugated diene block copolymer shown in Table 1, a molded product 7 was obtained in the same manner as in Example 1, and a transparency test and a high temperature and high humidity resistance test were obtained. Went. The results are shown in Table 2.

Table 2 shows the following.
The resin composition of the present invention, that is, a vinyl alicyclic hydrocarbon polymer (A) and a hydride (B) of an aromatic vinyl-conjugated diene block copolymer (b),
The aromatic vinyl-conjugated diene block copolymer (b) before hydrogenation is
1) It consists of a polymer block (i) composed of a repeating unit derived from an aromatic vinyl compound and a polymer block (ii) composed of a repeating unit derived from a conjugated diene compound,
2) The polymer block (ii) has 40% by weight or more of the repeating units derived from the conjugated diene compound constituting the repeating unit which are subjected to 1,2-addition polymerization and 3,4-addition polymerization. And 3) A molded product obtained by molding a resin composition having a hydroxyl group at the end of the main chain is excellent in transparency and resistance to high temperature and high humidity (Examples 1 to 4).

  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 of an aromatic vinyl-conjugated diene block copolymer (E5) not modified with a hydroxyl group is excellent in transparency, but is resistant to high temperatures and high humidity. (Comparative Example 2). Furthermore, the aromatic vinyl in which the proportion of the repeating unit derived from 1,2- and 3,4-addition polymerization in the repeating unit derived from the conjugated diene compound of the conjugated diene block (II) is not more than 40% by weight It can be seen that a molded product obtained by molding a resin composition using a hydride (E6) of a conjugated diene block copolymer is excellent in high temperature and high humidity resistance but poor in transparency (Comparative Example 3).

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

Claims (14)

A vinyl alicyclic hydrocarbon polymer (A) and a hydride (B) of an aromatic vinyl-conjugated diene block copolymer (b),
The aromatic vinyl-conjugated diene block copolymer (b) before hydrogenation is
1) It consists of a polymer block (i) composed of a repeating unit derived from an aromatic vinyl compound and a polymer block (ii) composed of a repeating unit derived from a conjugated diene compound,
2) The polymer block (ii) has 40% by weight or more of repeating units obtained by 1,2-addition polymerization and 3,4-addition polymerization in the repeating units derived from the conjugated diene compound constituting the polymer block (ii), And 3) having a hydroxyl group at the end of the main chain,
The resin composition characterized by the above-mentioned.   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.   The polymer (A) is obtained by hydrogenating 80 mol% or more of all carbon-carbon unsaturated bonds including an aromatic ring in the polymer (a) having a repeating unit derived from an aromatic vinyl compound. 2. The resin composition according to 1.   The resin composition according to claim 1, wherein the polymer (A) has a glass transition temperature of 80 to 250 ° C.   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 / number average molecular weight) of 5 or less.   The resin composition according to claim 1, wherein the block copolymer (b) has a hydroxyl group of 50 mol% or more at the terminal of the main chain.   The resin composition according to claim 1, wherein the block copolymer (b) is composed of a polymer block (i) -polymer block (ii) -polymer block (i).   The resin composition according to claim 1, wherein the ratio of the polymer block (i) in the block copolymer (b) is 15 to 55% by weight.   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 bond in the polymer block (ii) The resin composition according to claim 1, wherein 60 mol% or more is hydrogenated.   The resin composition according to claim 1, wherein the hydride (B) has a glass transition temperature of 30 ° C. or lower.   The resin composition according to claim 1, wherein the hydride (B) is 0.001 to 50 parts by weight with respect to 100 parts by weight of the polymer (A). The refractive index _n D of the polymer (A) (A), the resin composition according to claim 1 the absolute value of the difference between the refractive index _n D (B) is 0.01 or less hydride (B) .   The molded object formed by shape | molding the resin composition of Claim 1.   The molded article according to claim 13 which is a lens.