KR20120022561A - Curable resin composition and cured product thereof - Google Patents

Abstract

PURPOSE: A curable resin composition is provided to have excellent optical properties and to have excellent the balance of various properties needed for an optical lens or prism material. CONSTITUTION: A curable resin composition comprises a soluble polyfunctional (meth)acrylic acid ester copolymer, and a monomer including at least one functional group containing polymerizable unsaturated double bond. The copolymer is manufactured through the copolymerization of monofunctional (meth)acrylic acid ester with a cycloaliphatic structure, a monofunctional (meth)acrylic acid ester with alcoholic hydroxy group, bifunctional (meth)acrylic acid ester, and 2,4-diphenyl-4-methyl-1-pentene. The side chain of the copolymer comprises a reactive (meth)acrylate group originated from the bifunctional (meth)acrylic acid ester, and the end of the chain comprises a repeating unit from 2,4-diphenyl-4-methyl-1-pentene.

Description

Curable resin composition and its hardened | cured material {CURABLE RESIN COMPOSITION AND CURED PRODUCT THEREOF}

The present invention has excellent optical properties such as low color dispersion and high light transmittance, heat resistance and workability, and also has optical properties, low absorption and inorganic properties under harsh practical conditions such as wet heat conditions. The present invention relates to a curable resin composition having improved adhesion to materials and a cured product thereof.

 Most of the monomers having an unsaturated bond with reactive activity are capable of producing a multimer by selecting an appropriate reaction condition and a catalyst causing the unsaturated bond to cleave, resulting in a chain reaction. Generally, since the kind of monomer which has an unsaturated bond varies widely, the richness of the kind of resin obtained is also remarkable. However, there are relatively few kinds of monomers capable of obtaining a high molecular weight of 10,000 or more, generally referred to as a high molecular compound. For example, ethylene, substituted ethylene, propylene, substituted propylene, styrene, alkyl styrene, alkoxy styrene, norbornene, various acrylic esters, butadiene, cyclopentadiene, dicyclopentadiene, isoprene, maleic anhydride, maleimide , Fumaric acid ester, allyl compound, etc. are mentioned as a typical monomer. Various resins are synthesize | combined by these monomers being independent or copolymerizing them.

The use of these resins is mainly limited to the field of relatively inexpensive domestic appliances, and in the field of optoelectronic materials, there are few applications in the high-tech fields that require high heat resistance, dimensional stability and fine workability. The reason is that the polymer synthesized from the above-mentioned monomers is usually thermoplastic, and in order to satisfy the mechanical properties, it is necessary to make a substantial high molecular weight, so that the characteristics required in the high-tech fields such as heat resistance and fine workability are sacrificed. Can be mentioned.

On the other hand, curable resin composition is useful as a mechanical component material, an electrical / electronic component material, an automotive component material, a civil engineering building material, a molding material, etc., and is used also as a material of a coating material and an adhesive agent. Furthermore, when the hybrid member is combined with an inorganic substrate, not only can the thermal expansion coefficient be lowered, but also the refractive index between the inorganic substance and the resin can be adjusted to control the appearance of the resin composition and the cured product so that transparency can be expressed. It is particularly useful as a material in electrical and electronic component materials and optical applications. For example, the digital camera module is being miniaturized such as being mounted in a mobile phone, and the cost is also required. Further, as new applications, there is an increasing need for in-vehicle cameras and bar code readers for parcel delivery companies. When applied to these uses, not only the heat resistance at the time of solder reflow at the time of manufacture is required, but also the high reliability of long-term heat resistance, low water absorption, etc. is calculated | required in consideration of high temperature exposure in summer at the time of actual use.

As a method of solving the drawback of such a vinyl-based thermoplastic polymer, Patent Documents 1 to 3 disclose a polymer having a (meth) acryloyl group or a vinyl ether group in a pendant. For example, Patent Document 1 discloses a photosensitive composition comprising a (meth) acryloyl group pendant polymer obtained by cationic polymerization of heteropolymerizable monomers such as 2-vinyloxyethyl acrylate (VEA) and a photopolymerization initiator. . In addition, Patent Document 2 discloses a photosensitive composition comprising a (meth) acryloyl group pendant polymer, a compound having a photoreactive unsaturated carboxyl group, and a photopolymerization initiator. In addition, Patent Document 3 discloses a heteropolymerizable monomer such as 2-vinyloxyethyl acrylate (VEA) alone using a cationic polymerization catalyst in a carboxylic ester solvent compound having a photoreactive unsaturated group which is inert to its own cationic polymerization. A method for producing a polymer solution by polymerizing or copolymerizing is disclosed.

However, when using a reactive polymer prepared according to the technique using the heteropolymerizable monomer disclosed in these documents, the balance of properties such as low absorption, moldability, heat resistance and high transparency required in the field of advanced optical lens prism applications can be achieved. In addition, polymers and curable resin compositions in which optical properties and adhesion to inorganic materials were improved under harsh actual conditions such as wet heat conditions were not obtained.

On the other hand, in patent document 4, it is obtained by copolymerizing a monovinyl aromatic compound and a bifunctional (meth) acrylic acid ester, and is soluble polyfunctional which has a structural unit containing the reactive (meth) acrylate group derived from bifunctional (meth) acrylic acid ester in a side chain. Vinyl aromatic copolymers are disclosed. However, the soluble polyfunctional vinyl aromatic copolymer obtained by the technique disclosed in this document has excellent thermal decomposition resistance against thermal history at high temperature, has a reactive (meth) acrylate group in the side chain, and is excellent in processability and solvent solubility. Although it has a practical use limitation that it cannot be used for the optical lens for low chromatic dispersion use, it was a material which did not improve adhesiveness with an inorganic material.

Further, Patent Document 5 contains 1 to 25% by weight of di (meth) acrylate of a linear aliphatic dihydric alcohol having 4 to 8 carbon atoms as a constituent in methyl methacrylate (MMA) syrup. A composition is disclosed. In the preparation of the MMA syrup composition disclosed in this document, MMA or a vinyl copolymer capable of copolymerizing with MMA and a chain copolymer, and a chain transfer agent in the presence of a polymerization initiator, in an inert gas (for example, N ² gas) atmosphere, It is disclosed to carry out at room temperature or by heat polymerization. Specific examples of the chain transfer agent in the document include sulfur compounds such as lauryl mercaptan, thioglycolic acid octyl ester, thicresol, thionaphthol and benzyl mercaptan, and 2,4-diphenyl-4-methyl-. 1-pentene (hereinafter also referred to as DMP) is not specifically disclosed. Furthermore, by the coexistence of the structural unit derived from the monofunctional (meth) acrylic acid ester (a) which has the terminal group derived from DMP, and the alicyclic structure which has an alicyclic structure, it can synergistically suppress generation | occurrence | production of the refractive index branching in wet heat. Not even a preview. Moreover, the composition obtained by the technique disclosed in this document did not improve the adhesiveness with the inorganic material under the harsh practical conditions such as wet heat conditions.

In addition, Patent Document 6 discloses a polymerizable composition composed of a vinyl monomer and a di (meth) acrylate compound, and although the use of DMP is also disclosed, the amount of use thereof is about a few percent comma as a conventional chain transfer agent. The product was also crosslinked and gelled to show no solvent solubility.

In addition, Patent Literature 7 discloses a porcelain comprising a structural unit comprising 1) an epoxy group-containing (meth) acrylate, 2) a hydroxyl group-containing (meth) acrylate, 3) (meth) acrylic acid, and 4) aromatic group-containing (meth) acrylate. A thermosetting resin composition for color filters comprising a curable copolymer and an organic solvent is disclosed. In addition, the self-curable copolymer obtained by the technique disclosed in this document is a mercaptopropionic acid, a mercaptopropionic acid ester, thioglycol, thioglycerine, dodecyl mercaptan, α in the polymerization step in order to achieve a preferred range of molecular weight. It is disclosed that known molecular weight regulators such as -methyl styrene dimer can be used. However, in the technique disclosed in this document, since at least one bifunctional or more vinyl compound having a plurality of vinyl groups is not added at the time of polymerization, only a terminal group derived from one or less molecular weight regulators can be introduced into the polymer chain, and thus a function derived from a terminal group. There was a flaw that it could not be given enough. In addition, in this document, although the self-curable copolymer obtained by the technique disclosed forms a thermosetting resin composition in the resin composition with an epoxy resin, since hardening reaction does not arise between an acrylate resin, There also existed a fault that the intensity | strength and heat resistance fall of the mix | blended resin composition are caused.

Therefore, it has excellent optical characteristics such as low color dispersion and high light transmittance, and has a balance of characteristics such as low absorption, moldability, and heat resistance, and optical properties, low absorption, heat resistance, and inorganic materials under harsh practical conditions such as wet heat conditions. The curable resin composition which the adhesiveness of the improved was not existed until now.

Japanese Patent Publication No. 49-13212 Japanese Patent Publication No. 51-34433 Japanese Patent Publication No. 54-27394 Japanese Unexamined Patent Publication No. 2008-247978 Japanese Laid-Open Patent Publication No. 57-167340 Japanese Patent Laid-Open No. 2002-121228 Japanese Unexamined Patent Publication No. 2009-1770

The present invention has excellent optical properties such as low color dispersion and high light transmittance, excellent balance of properties required for optical lens and prism materials in advanced technology fields such as low absorbency, processability, and heat resistance, and also has a tough seal such as wet heat conditions. An object of the present invention is to provide a curable resin composition having improved optical properties and adhesion with an inorganic material under use conditions.

The present invention

(A) component: Monofunctional (meth) acrylic acid ester (a) which has alicyclic structure, Monofunctional (meth) acrylic acid ester (b) which has an alcoholic hydroxyl group, bifunctional (meth) acrylic acid ester (c), 2, As a copolymer obtained by copolymerizing the component containing 4-diphenyl-4-methyl-1- pentene (d), it has a reactive (meth) acrylate group derived from bifunctional (meth) acrylic acid ester (c) in a side chain, It is a copolymer which has a structural unit derived from 2, 4- diphenyl-4-methyl-1- pentene (d) at the terminal, has a weight average molecular weight of 2000-50000, and also toluene, xylene, tetrahydrofuran, dichloroethane, or Soluble polyfunctional (meth) acrylic acid ester copolymer soluble in chloroform, and

(B) component: Monomer which has one or more functional groups which have a polymerizable unsaturated double bond

As a resin composition which uses as an essential component, the compounding quantity of (A) component with respect to the sum total of (A) component and (B) component is 1-70 wt%, and the compounding quantity of (B) component is 99-30 wt%, It is characterized by the above-mentioned. Curable resin composition.

The amount of 2,4-diphenyl-4-methyl-1-pentene (d) introduced into the component (A) is preferably 0.02 to 0.35 as the mole fraction (M _d ) represented by the following formula (1). Moreover, it is preferable that the introduction amount into the side chain of the reactive (meth) acrylate group derived from bifunctional (meth) acrylic acid ester (c) is 0.05-0.5 as mole fraction ( _Mc1 ) represented by following formula (2).

Also preferred that the introduced amount of the monofunctional (meth) acrylate (b) having an alcoholic hydroxyl group in the component (A), the following equation (3) mole fraction (M _b) as 0.05? 0.60 represented by, and also as the molar fraction (M _a) represented by the monofunctional (meth) introduced amount is, the formula of the acrylate ester (a) (4) having an alicyclic structure is preferably 0.05? 0.60.

M _d = (d) / [(a) + (b) + (c) + (d)] (1)

M _c1 = (c1) / [(a) + (b) + (c)] (2)

M _b = (b) / [(a) + (b) + (c)] (3)

M _a = (a) / [(a) + (b) + (c)] (4)

Here (a), (b), (c) and (d) are a monofunctional (meth) acrylic acid ester which has a structural unit derived from the monofunctional (meth) acrylic acid ester (a) which has an alicyclic structure, and an alcoholic hydroxyl group ( The number of moles of the structural unit derived from b), the structural unit derived from the bifunctional (meth) acrylic acid ester (c), and the structural unit derived from 2,4-diphenyl-4-methyl-1-pentene (d) Indicates. In addition, (c1) shows the number-of-moles of the structural unit containing a bifunctional (meth) acrylate group in a side chain.

As monofunctional (meth) acrylic acid ester (a) which has the said alicyclic structure, isobonyl methacrylate, isobonyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, dicyclopentenyl acrylate, dicyclophene At least one alicyclic group selected from the group consisting of tenyloxyethyl acrylate, dicyclopentanyl acrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentenyloxyethyl methacrylate, and dicyclopentanyl methacrylate Monofunctional (meth) acrylic acid ester which has a structure is mentioned preferably.

As said monofunctional (meth) acrylic acid ester (b) which has the said alcoholic hydroxyl group, the group which consists of 2-hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate, and the 2-ethoxylated 2-hydroxy methacrylate The monofunctional (meth) acrylic acid ester chosen from is mentioned preferably.

As said bifunctional (meth) acrylic acid ester (c), 1, 4- butanediol diacrylate, 1, 6- hexanediol diacrylate, 1, 9- nonane diol diacrylate, and dimethylol tricyclodecane diacrylate 1 or more types of bifunctional (meth) acrylic acid ester chosen from the group which consists of these are mentioned preferably.

As a monomer or oligomer which has one or more functional groups which have an unsaturated double bond of the said B component, 1 or more types of (meth) acrylic acid chosen from monofunctional (meth) acrylic acid ester and bifunctional (meth) acrylic acid ester which have an alicyclic structure Ester is mentioned preferably.

It is preferable that curable resin composition of this invention contains a photoinitiator further as (C) component.

Moreover, this invention is obtained by hardening | curing said curable resin composition, It is a hardened | cured material characterized by the above-mentioned. Furthermore, this invention is an optical material characterized by being formed from said hardened | cured material. As said optical material, an optical plastic lens or a prism is mentioned preferably.

According to the present invention, it has excellent optical properties such as low color dispersion and high light transmittance, and is excellent in the balance of various properties required for optical lens and prism materials in advanced technical fields such as low absorption, workability, and heat resistance. The curable resin composition which improved the adhesiveness of an optical property and an inorganic material under severe actual conditions can be provided.

Hereinafter, the curable resin composition of this invention is demonstrated in detail.

Soluble polyfunctional (meth) acrylic acid ester copolymer (henceforth a copolymer) which is (A) component of this invention is a monofunctional (meth) acrylic acid ester (a) which has an alicyclic structure, Air obtained by copolymerizing a monomer containing a functional (meth) acrylic acid ester (b) and a bifunctional (meth) acrylic acid ester (c) with 2,4-diphenyl-4-methyl-1-pentene (d). Structural unit which has a reactive (meth) acrylate group derived from bifunctional (meth) acrylic acid ester (c) in a side chain as a copolymer, and originates in 2, 4- diphenyl-4-methyl-1- pentene (d) at the terminal. It is a soluble polyfunctional (meth) acrylic acid ester copolymer which has a. Soluble here means soluble in toluene, xylene, tetrahydrofuran, dichloroethane or chloroform. Solubility test consists of conditions shown in the synthesis example. On the other hand, monofunctional (meth) acrylic acid ester has one number of ethylenic double bonds in a molecule, and bifunctional (meth) acrylic acid ester has two number of ethylenic double bonds in a molecule, and polyfunctional (meth) acrylic acid It is understood that the ester copolymer has two or more ethylenic double bonds present in the molecule. Moreover, the monofunctional (meth) acrylic acid ester (a) which has an alicyclic structure (a) component, and the monofunctional (meth) acrylic acid ester (b) which has an alcoholic hydroxyl group are (b) component, and bifunctional (meth) acrylic acid ester ( c) (c) component and 2, 4- diphenyl- 4-methyl- 1-pentene (d) are also called (d) component or DMP.

Since the copolymer is obtained by copolymerizing a monofunctional (meth) acrylic acid ester and a bifunctional (meth) acrylic acid ester, the copolymer has a branched structure or a crosslinked structure, and the amount of such a structure is limited to the extent of showing solubility. Therefore, it becomes a copolymer which has in a side chain the structural unit (c1) containing the unreacted (meth) acryl group derived from bifunctional (meth) acrylic acid ester (c). This unreacted (meth) acryl group is also called a pendant (meth) acryl group, and since it shows polymerizability, it can superpose | polymerize by further polymerization process and can provide the resin hardened | cured material of a solvent insoluble.

In addition, a copolymer has a structural unit derived from (d) component at the terminal. By introducing this structural unit at the terminal of the copolymer, a cured product having improved moldability such as mold release property can be obtained.

The copolymer has a structural unit derived from the component (a), a unit derived from the component (b), a structural unit derived from the component (c), and a structural unit derived from the component (d). The structural unit derived from component (c) is a structural unit in which both polymerizable double bonds (called vinyl groups) contained in two (meth) acrylic acid esters are involved in polymerization to form a branched structure or a crosslinked structure (c2). ) And a structural unit (c1) containing an unreacted (meth) acryl group, in which only one vinyl group is involved in polymerization and the other vinyl group does not react. DMP as a component (d) acts as a chain transfer agent to prevent an increase in molecular weight and is present at the end of the copolymer.

The amount of the component (d) introduced into the copolymer is 0.02 to 0.35, preferably 0.03 to 0.30, and particularly preferably 0.05 to 0.15 as the mole fraction (M _d ) represented by the following formula (1).

M _d = (d) / [(a) + (b) + (c) + (d)] (1)

Here, (a), (b), (c) and (d) represent the number of moles of the structural unit derived from each component of (a), (b), (c) and (d). By introducing the structural unit derived from (d) component in the said range at the terminal of a copolymer, mold release property and low water absorption can be improved.

The bifunctional (meth) acrylic acid ester (c) branches or crosslinks the copolymer and simultaneously forms a pendant vinyl group to impart curability to the copolymer, and plays an important role as a crosslinking component for expressing heat resistance upon curing. .

As bifunctional (meth) acrylic acid ester, cyclohexane dimethanol diacrylate, dimethylol tricyclodecane diacrylate, cyclohexane dimethanol dimethacrylate, dimethylol tricyclodecane dimethacrylate, ethylene glycol diacrylate, Propylene glycol diacrylate, 1,4-butanediol diacrylate, hexanediol diacrylate, diethylene glycol diacrylate, ethylene glycol diacrylate, propylene glycol diacrylate, 1,4-butanediol dimethacrylate, Although bifunctional (meth) acrylic acid ester, such as hexanediol dimethacrylate and diethylene glycol dimethacrylate, can be used, It is not limited to these.

As a preferable specific example of bifunctional (meth) acrylic acid ester, cyclohexane dimethanol diacrylate and dimethylol tricyclodecane diacrylate are used preferably from a cost, the ease of superposition | polymerization control, and the heat resistance of the obtained polymer.

The copolymer has a structural unit (c1) containing a reactive (meth) acrylate group derived from a bifunctional (meth) acrylic acid ester (c) in the side chain, and the mole fraction of the structural unit (c1) represented by the formula (2) It is preferable that ( _Mc1 ) is 0.05 or more and 0.5 or less, Preferably it is 0.1-0.3.

M _c1 = (c1) / [(a) + (b) + (c)] (2)

Here, (c1) shows the number-of-moles of the structural unit (c1) containing a (meth) acrylate group. By satisfy | filling the said mole fraction, the molded article which is rich in sclerosis | hardenability in light and heat, and excellent in the heat resistance after hardening and a mechanical characteristic can be obtained.

The structural unit derived from the bifunctional (meth) acrylic acid ester (c) may include the structural unit (c1) and other structural units, but all of the structures derived from the bifunctional (meth) acrylic acid ester (c) the mole fraction of units _(c) (M c) of 0.1? 0.7, preferably 0.15? preferably 0.65.

M _c = (c) / [(a) + (b) + (c)] (5)

Monofunctional (meth) acrylic acid ester (a) having an alicyclic structure is important for improving solvent solubility, low water absorption, heat resistance, optical properties and processability of the copolymer. As monofunctional (meth) acrylic acid ester which has such an alicyclic structure, isobornyl methacrylate, isobonyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, dicyclopentenyl acrylate, dicyclopentenyl oxyethyl acryl Monofunctional having at least one alicyclic structure selected from the group consisting of latex, dicyclopentanyl acrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentenyloxyethyl methacrylate, and dicyclopentanyl methacrylate Although (meth) acrylic acid ester is mentioned, It is not limited to these. Since the structural unit derived from these components is introduced into the copolymer having an alicyclic structure, it is possible to prevent the gelation of the polymer and to increase the solubility in the solvent, as well as optical properties such as low color dispersion of the copolymer, low absorption, Heat resistance can be improved.

As monofunctional (meth) acrylic acid ester (a) which has a preferable alicyclic structure, the compound represented by a following formula (a1) is mentioned.

A-R-C- (R ') n (a1)

A is a (meth) acryloxy group, R is a single bond or a C1-C10 alkylene group or a polyalkylene oxide group, C is an aliphatic ring, R 'is a C1-C10 substituent substituted by an aliphatic ring It is an alkyl group and n is 0-5.

As monofunctional (meth) acrylic acid ester (a) which has another preferable alicyclic structure, the compound represented by a following formula (a2) is mentioned.

R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrocarbon group having an alicyclic structure of 6 to 15 carbon atoms, R ³ represents an alkylene group of 2 to 4 carbon atoms, m represents an integer of 0 to 10 Indicates.

Preferred embodiments include isobornyl methacrylate, isobornyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, dicyclopentenyl acrylate and dicyclopentenyl oxy in terms of cost, gelling prevention and molding processability of the obtained polymer. Having at least one alicyclic structure selected from the group consisting of ethyl acrylate, dicyclopentanyl acrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentenyloxyethyl methacrylate, and dicyclopentanyl methacrylate Monofunctional (meth) acrylic acid ester is mentioned.

The monofunctional (meth) acrylic acid ester (b) having an alcoholic hydroxyl group is important for improving the adhesion with the inorganic material under harsh practical use conditions such as wet heat conditions of the copolymer. As monofunctional (meth) acrylic acid ester which has such an alcoholic hydroxyl group, 2-hydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxy Butyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, and partially ethoxylated 2-hydroxy (meth) acrylate, and the like, although preferred. Preferably 2-hydroxyethyl methacrylate. The (meth) acrylic acid ester monomer which has these alcoholic hydroxyl groups may be used independently, or may use two or more types together.

As monofunctional (meth) acrylic acid ester (b) which has a preferable alcoholic hydroxyl group, the compound represented by a following formula (b1) is mentioned.

R ¹ represents a hydrogen atom or a methyl group, and R ⁴ represents a hydrocarbon group having one hydroxyl group having 2 to 6 carbon atoms.

Monofunctional (meth) acrylic acid ester (b) containing an alcoholic hydroxyl group is a monofunctional (meth) acrylic acid ester (c) containing the mole fraction of (a) component, (b) component, and (c) component in an copolymer, and an alcoholic hydroxyl group (c). ) may be a M _b is the molar fraction of the structural unit derived from the represented by the formula (3) 0.05 or more, 0.60 or less, preferably 0.1? 0.3.

M _b = (b) / [(a) + (b) + (c)] (3)

Here, (a), (b) and (c) in the formula represent the number of moles of the structural unit derived from each component of (a), (b) and (c). By satisfy | filling the said mole fraction, the copolymer with a favorable balance which can improve the optical characteristic and adhesiveness with an inorganic material under harsh actual conditions, such as wet heat conditions, can be obtained.

In addition, M _a represented by the formula (4) is preferably 0.05 or more and 0.60 or less, and preferably 0.1 to 0.3.

DMP functions as a chain transfer agent and controls the molecular weight of the copolymer. The molecular weight of the copolymer is in the range of 2000 to 50000, preferably in the range of 3000 to 25000 as the weight average molecular weight (Mw). Moreover, it is preferable on the relationship with (B) component that Mw is the range of 6000-50000. The use of a relatively low molecular weight copolymer enhances the moldability and mold release property of the cured resin.

Moreover, it is possible to add monofunctional (meth) acrylic acid ester which does not have an alicyclic structure and a hydroxyl group as (e) component in order to improve the solvent solubility and processability of a copolymer. As such (meth) acrylic acid ester, methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-methylhexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, etc. And methyl methacrylate and n-butyl acrylate. These (meth) acrylic acid ester monomers may be used alone or in combination of two or more, but at least one (meth) acrylic acid selected from the group consisting of methyl methacrylate, methyl acrylate, and n-butyl acrylate Most preferably, it is an ester.

In addition, the structural unit derived from these other monomer components (e) is 30 mol% with respect to the total amount of the structural unit derived from the monomer component (a), the structural unit derived from the monomer component (b), and the structural unit derived from the monomer component (c). It is good to carry out within the range below.

Moreover, from another viewpoint, 20-55 mol% of structural units derived from (a) component, 20-35 mol% of structural units derived from (b) component, and soluble polyfunctional (meth) acrylic acid ester copolymer are derived from (c) component It is preferable to include 55-10 mol% of structural units, Preferably it is 50-12 mol%, More preferably, 40-15 mol%, and 2-35 mol% of structural units derived from (d) component. If the structural unit derived from the bifunctional (meth) acrylic acid ester (c) is less than 10 mol%, the heat resistance of the cured product is insufficient, and if the structural unit exceeds 55 mol%, the molding processability is lowered, and the strength of the molded product. Is not preferable because it is significantly lowered.

Moreover, it is good to set the structural unit derived from other monomer (e) component in less than 30 mol% with respect to the total amount of the structural unit derived from (a) component, and the structural unit derived from (b) component.

Although it does not specifically limit as a manufacturing method of the copolymer used as (A) component, It adjusts so that it may become desired content of DMP, two types of monofunctional acrylate ester aromatic compounds, and a bifunctional (meth) acrylic acid ester, and if necessary, radicals. It is produced by polymerization at a temperature of 20 to 200 ° C. using a polymerization initiator and a solvent, and is recovered by a commonly used method such as, for example, a steam stripping method or precipitation into a poor solvent.

This copolymer is soluble which melt | dissolves 1 g or more with respect to 100 g of said solvents. Preferably, it melt | dissolves 5g or more with respect to 100g of said solvent at 25 degreeC.

Next, (B) component is demonstrated.

As the component (B), a monomer having one or more functional groups having a polymerizable unsaturated double bond is used. Although the monomer as (B) component can be an oligomer here, it is not the same as the copolymer of (A) component. On the other hand, it is not the same thing that monofunctional (meth) acrylic acid ester (a) which has an alicyclic structure, monofunctional (meth) acrylic acid ester (b) which has an alcoholic hydroxyl group, bifunctional (meth) acrylic acid ester (c), It means that it is not a copolymer obtained by copolymerizing the component containing 2, 4- diphenyl-4-methyl-1- pentene (d). The oligomer may be a homopolymer or a copolymer, and the molecular weight (Mw) is preferably a low molecular weight polymer of 10000 or less, preferably 6000 or less, more preferably 5000 or less, and even more preferably 1000 or less. Moreover, the compound which does not have molecular weight distribution may be sufficient as the monomer as (B) component, and a some compound can be used in this case. Preferably it is a monomer whose molecular weight is 1000 or less. When the monomer is an oligomer, the molecular weight means Mw. Moreover, in the relationship with (A) component, it is preferable that the molecular weight (Mw) of the monomer of (B) component is lower than that in relationship with Mw of the copolymer of (A) component, and it is preferable that it is 1000 or more low.

The monomer has one or more functional groups having a polymerizable unsaturated double bond, and examples of the functional group having a polymerizable unsaturated double bond include a vinyl group and a (meth) acryloyl group.

The monomer as the component (B) is preferably a (meth) acrylate monomer. The (meth) acrylate monomer has one or more (meth) acryloyl groups in the molecule, and one kind or two or more kinds are used. By using together with (A) component, the (meth) acrylate used as these (B) components becomes possible to adjust the viscosity of a composition, without degrading sclerosis | hardenability, and synergistically, in addition to heat resistance, low color dispersion, high light transmittance, The same optical characteristic is improved at the same time. It is also possible to improve physical properties such as hardness and flexibility of the cured product.

The (meth) acrylate monomer is preferably a monomer having a molecular weight of 6000 or less, preferably 5000 or less, particularly 1000 or less. Moreover, the monomer (oligomer) which has molecular weight distribution like polyethyleneglycol di (meth) acrylate may be sufficient, In this case, Mw is 6000 or less, Preferably it is 5000 or less, More preferably, 2000 or less, Especially 1000 or less are good. Advantageously, these are monomers or mixtures thereof which consist of compounds having no molecular weight distribution.

As said (meth) acrylate monomer, what is copolymerizable with (A) component is good, For example, the (meth) acrylic acid ester which has an alicyclic structure is preferable, A monofunctional, bifunctional, or trifunctional (meth) acrylic acid ester is It is more preferable, and monofunctional (meth) acrylic acid ester is still more preferable. Moreover, as for the (meth) acrylate monomer as a B component, C4-20 aliphatic acrylate is preferable and it is good to have 1-3 unsaturated bonds derived from an acrylate. Since the (meth) acrylic acid ester having an alicyclic structure is excellent in compatibility with the component (A), the low absorption, heat resistance, optical properties and workability as the whole composition are increased by improving the component (A). effective. In addition, urethane-modified (meth) acrylates and ethylene oxide-modified (meth) acrylates are effective in improving the flexibility of the cured product. Furthermore, in order to improve the hardness of hardened | cured material, the (meth) acrylate monomer more than trifunctional is effective.

As a (meth) acrylate monomer, acryloyl morpholine, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, Polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, cyclohexane-1,4-dimethanol mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, phenoxyethyl (meth ) Acrylate, phenyl polyethoxy (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, o-phenylphenol monoethoxy (meth) acrylate, o-phenylphenol polyethoxy (Meth) acrylate, p-cumylphenoxyethyl (meth) acrylate, isobonyl (meth) acrylate, tribromophenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclophene Tenyl (meta) Acrylate, dicyclopentenyloxyethyl (meth) acrylate, 1,4-butanedioldi (meth) acrylate, 1,6-hexanedioldi (meth) acrylate, 1,9-nonanedioldi (meth) Acrylate, tricyclodecane dimethanol (meth) acrylate, bisphenol A polyethoxydi (meth) acrylate (for example, Saromer, SR-349, SR-348, etc.), bisphenol A poly Propoxydi (meth) acrylate, bisphenol F polyethoxydi (meth) acrylate, ethylene glycol di (meth) acrylate, trimethylolpropanetrioxyethyl (meth) acrylate, tris (2-hydroxyethyl) Isocyanurate tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, polyethylene glycol di (meth) acrylate (for example, from Sarmer Corporation, SR-344 , SR-268, etc.), tris (acryloxyethyl) Anurate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol Di (meth) acrylate of an ε-caprolactone adduct of penta (meth) acrylate, hydroxy pivalate neophenglycol di (meth) acrylate, and hydroxy pivalate neophenglycol (for example, Nippon Kayaku Co., Ltd.) ), KAYARAD HX-220, HX-620, etc.), trimethylolpropane tri (meth) acrylate, trimethylolpropanepolyethoxytri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, urethane modified And monomers such as (meth) acrylate (for example, Daicel-Cytec Co., Ltd. product, EBACRYL 8405, EBACRYL 8402, etc.). Especially preferably, 1, 6- hexanediol di (meth) acrylate, trimethylol propane tri (meth) acrylate, trimethylol propane trioxyethyl (meth) acrylate, pentaerythritol tri (meth) acrylate, di Pentaerythritol hexa (meth) acrylate, urethane modified (meth) acrylate, bisphenol A polyethoxy di (meth) acrylate, and ethylene glycol di (meth) acrylate are mentioned.

It is preferable that curable resin composition of this invention contains a polymerization initiator, Preferably a photoinitiator as (C) component. Although the curable resin composition of this invention can be shape | molded and hardened | cured even by thermal polymerization, when shape | molding and hardening optical materials, such as a lens, photocurable which can control shape strictly is advantageous, and therefore, it is preferable to add a photoinitiator.

As a photoinitiator of (C) component, For example, benzoin, such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether; Acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropane-1 Acetophenones, such as -one, diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one; Anthraquinones such as 2-ethylanthraquinone, 2-teraryl butylanthraquinone, 2-chloroanthraquinone and 2-amylanthraquinone; Thioxanthones, such as 2, 4- diethyl thioxanthone, 2-isopropyl thioxanthone, and 2-chloro thioxanthone; Ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzophenones such as benzophenone, 4-benzoyl-4'-methyldiphenylsulfide and 4,4'-bismethylaminobenzophenone; Phosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide.

These can be used individually or as a mixture of 2 or more types, Furthermore, tertiary amines, such as a triethanolamine and a methyl diethanolamine, N, N- dimethylamino benzoic acid ethyl ester, N, N- dimethylamino benzoic acid isoamyl ester, etc. It can be used in combination with accelerators, such as a benzoic acid derivative.

Curable resin composition of this invention contains the said (A) component and (B) component as an essential component, The content rate is as follows. The compounding quantity of (B) component is 99-30 weight part with respect to a total of 100 weight part of the compounding quantity of (A) component and (B) component, Preferably it is 90-30 weight part, More preferably, it is 60-45 weight part . In addition, when it contains (C) component, the compounding quantity of (C) component is 0.1-10 weight part with respect to a total of 100 weight part of the compounding quantity of (B) component and (A) component, Preferably it is 1.0-5 weight part. .

From another viewpoint, it is good to contain (A) component: 1-69 wt%, (B) component: 30-98 wt%, and (C) component: 0.1-10 wt%, respectively, in curable resin composition. More preferably, they are (A) component: 25-60 wt%, (B) component: 39-74 wt%, and (C) component: 1-5 wt%. Since the compounding ratio of (A) component, (B) component, and (C) component exists in the said range, the balance of the characteristic with the moldability, heat resistance, and optical characteristic shown synergistically to mold release property and curability is improved. If the component (C) is too small, hardening shortage is likely to occur, and heat resistance and light resistance are lowered. If too large, the mechanical strength or the heat resistance is lowered. On the other hand, when an organic solvent and a filler are included in curable resin composition, the said content is computed except these.

Moreover, the curable resin composition of this invention contains a polymerization inhibitor, antioxidant, a mold release agent, a photosensitizer, an organic solvent, a silane coupling agent, a leveling agent, an antifoamer, an antistatic agent, and also a ultraviolet absorber, a light stabilizer, an inorganic, organic as needed. It is also possible to add various fillers, an antifungal agent, an antibacterial agent, etc. to the curable resin composition of this invention, and to provide the target functionality respectively.

Curable resin composition of this invention can be obtained by mixing the said (A) component, (B) component and (C) component, and other components in arbitrary order as needed. Curable resin composition of this invention is stable over time.

Curable resin composition of this invention can obtain hardened | cured material by irradiating active energy rays, such as an ultraviolet-ray. As a specific example of the light source used when irradiating and hardening an active energy ray here, for example, a xenon lamp, a carbon arc, a germicidal lamp, a fluorescent lamp for ultraviolet rays, a high pressure mercury lamp for radiation, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, an electrode Lamps, metal halide lamps, or electron beams by scanning or curtain-type electron beam accelerators. Moreover, when hardening curable resin composition of this invention by ultraviolet irradiation, about 300-20000mJ / cm <2> of the ultraviolet irradiation amount required for hardening is good. On the other hand, in order to fully harden a resin composition, it is preferable to irradiate active energy rays, such as an ultraviolet-ray, in inert gas atmospheres, such as nitrogen gas.

Moreover, the curable resin composition of this invention can use together additives, such as a silane coupling agent, a polymerization inhibitor, a leveling agent, a surface lubricant, an antifoamer, an optical stabilizer, antioxidant, a plasticizer, an antistatic agent, a filler, a solvent, etc. as needed. .

The hardened | cured material of curable resin composition of this invention can be obtained by irradiating active energy rays, such as an ultraviolet-ray and a visible light laser, in accordance with a conventional method. When using ultraviolet rays, irradiation is performed using low or high pressure mercury lamps, ultra high pressure mercury lamps, metal halide lamps, and xenon lamps. Especially as a light source, the lamp of 350-450 nm with strong energy intensity is preferable.

It is preferable that the refractive index of the hardened | cured material of the curable resin composition of this invention obtained by irradiating active energy rays, such as an ultraviolet-ray, is 1.49 or more at 25 degreeC, More preferably, it is 1.51 or more at 25 degreeC. When producing a prism lens sheet with the resin composition for optical materials of this invention especially, when the refractive index of hardened | cured material is less than 1.49 at 25 degreeC, there exists a problem that sufficient front brightness cannot be ensured.

Moreover, it is preferable that the Abbe number of hardened | cured material (the numerical value inherent in the substance which defines the property which changes the refractive index according to the wavelength of light) is 40.0 or more, More preferably, it is 50.0 or more. It is not preferable that the Abbe number of the cured product is less than 40.0 because chromatic aberration is large and color bleeding occurs.

The resin cured material obtained by shape | molding and hardening curable resin composition of this invention is excellent as optical materials, such as a prism and a lens. In particular, it is useful as a material for optical plastic lenses, such as a prism lens sheet, a fresnel lens, a lenticular lens, a spectacle lens, and an aspherical lens. And such lenses are advantageously used in imaging devices. The curable resin composition or cured resin can also be used for optoelectronics such as optical disks, optical fibers, optical waveguides, printing inks, paints, clear coatings, gloss varnishes, hard coatings, and the like.

Moreover, although the hardened | cured material of curable resin composition of this invention can also be used as an adhesive layer, As an article which has such an adhesive layer, a mobile telephone, a portable game machine, a digital camera, etc. are mentioned, for example.

When joining a polarizing film and a protective plate using the curable resin composition of this invention, it is not limited to the protective plates, such as an alkali free glass and quartz glass which are excellent in active energy ray permeability, for example, An acryl plate, polycarbonate, etc. which have large ultraviolet absorption Even the protective plate of can be used because of the good reaction curability of the composition.

Curable resin composition of this invention is apply | coated so that adhesive film thickness may be set to 1-100 micrometers using base materials, such as a roll coater, a spin coater, and the screen printing method, to base materials, such as a polarizing film, bonding a protective plate, and ultraviolet-ray on a protective plate. It can bond by irradiating and hardening.

<Examples>

Next, although an Example demonstrates this invention, this invention is not restrict | limited by these. In addition, all the parts in each case are a weight part. In addition, the measurement of each physical property in an Example performed the sample preparation and the measurement by the method shown below.

1) Molecular weight and molecular weight distribution of polymer

The molecular weight and molecular weight distribution of the soluble polyfunctional (meth) acrylic acid ester copolymer were measured using GPC (TOSO, HLC-8120GPC), solvent: tetrahydrofuran (THF), flow rate: 1.0 ml / min, column temperature: 40 It was carried out at ℃. The molecular weight of the copolymer was measured as a polystyrene reduced molecular weight using a calibration curve by monodisperse polystyrene.

2) polymer structure

It was determined by 13C-NMR and 1H-NMR analysis and elemental analysis using a JNM-LA600 type nuclear magnetic resonance spectrometer manufactured by Nippon Denshi. Chloroform-d1 was used as a solvent, and the resonance line of tetramethylsilane was used as an internal standard.

3) availability test

To 100 ml of various organic solvents (toluene, xylene, tetrahydrofuran, dichloroethane and chloroform) at 25 ° C., 1 g of the copolymer was added, and after 30 minutes of stirring using a magnetic stirrer, the solubility was visually confirmed. . It melt | dissolved in all the said organic solvents, and the case where the formation | generation of a gel is not recognized was made into solubility: (circle).

4) Preparation of test piece for physical property measurement

A curable composition is injected into a glass frame which is wound between two glass plates having a width of 50 mm, a length of 50 mm, and a thickness of 1.0 mm with a gap of 0.2 to 1.0 mm and fixed with a polyimide tape, and the cured composition is poured into the glass frame. After irradiating ultraviolet rays for 5 seconds with a high-pressure mercury lamp, the glass frame was cured by heating in an inert gas oven under a nitrogen gas stream for 1 hour. The resin plate hardened | cured from the glass frame was demolded, and was used for the measurement of various physical properties.

5) Measurement of refractive index

The refractive index and Abbe number in 589 nm were measured with the Abbe refractometer (Atago Co., Ltd. product).

6) Color (YI)

The flat plate of thickness 1.0mm was measured with the color difference meter (MODEL TC-8600 by Tokyo Denshoku Co., Ltd.), and the YI value was shown.

7) Haze (turbidity) and total light transmittance

A 0.2 mm-thick test piece was produced, and the Haze (turbidity) and total light transmittance of the sample were measured using an integrated sphere light transmittance measuring apparatus (SZ-∑90, manufactured by Nippon Denshoku Co., Ltd.).

8) Release property: The cured resin was evaluated according to the difficulty of releasing the mold from the mold.

○…. Good mold release

Δ. Molding is somewhat difficult

×… Mold release is difficult or mold remains

9) Frame reproducibility: The surface shape of the cured resin layer and the surface shape of the frame were observed.

○…. Good reproducibility

Δ. Good reproducibility depending on curing conditions (light and heat)

×… Poor reproducibility

10) Burr, Leakage: The cured resin was evaluated by releasing the cured resin from the mold depending on the size of the burr generated in addition to the product part of the molded product and the degree of resin leakage into the clearance of the mold.

○…. The amount of burr produced is less than 0.05 mm, and the degree of resin leaking into the frame clearance is less than 1.0 mm.

Δ. The amount of burr produced is not less than 0.05 mm and less than 0.2 mm. The degree of resin leaking into the frame clearance is 1.0 mm or more and less than 3.0 mm.

×… Burr formation is 0.2mm or more, and resin leaks into the frame clearance is 3.0mm or more.

11) Reflow heat resistance: The 1-mm-thick flat plate was used as a test piece, and the spectral transmittance of wavelength: 400 nm was measured with the spectrophotometer CM-3700d (made by Konica Minolta). The measurement timing was made before the heat test which performed postcure at 180 degreeC for 60 minutes, and after the heat test for 8 minutes at 260 degreeC in an air oven.

12) Absorption rate

A test piece weighing 1 mm thick flat plate, vacuum dried at 60 ° C. for 24 hours was Wo, and weighed to a balance of ± 0.1 mg. Temperature: 85 ° C., relative humidity: 85% Humidification was performed for 1 week in the bath. After moisturizing, the water on the test sample was wiped off, and the sample was weighed on a scale that could measure up to ± 0.1 mg. The water absorption was calculated by the following formula. Three identical test samples were prepared and tested identically.

Wo / W × 100 = absorption rate

13) Heat cycle resistance

The sample bonded by alkali-free glass (thickness; 0.7mm) and 2mm-thick acrylic plate with a thickness of 25µm using a 157mW ultra-high pressure mercury lamp at 3000mJ was cycled for 30 minutes at -35 ° C, 30 minutes at 85 ° C, and 30 minutes at 85 ° C. After performing 100 cycles on the conditions of minutes, the peeling state of two board | substrates was observed, and (circle) and no peeling were evaluated as (x).

14) moisture resistance

Two pieces of samples after leaving an alkali-free glass (thickness; 0.7 mm) and a 2 mm thick acrylic plate bonded to a thickness of 25 µm using an ultra-high pressure mercury lamp of 157 mW at 25 m thickness for 100 hours at 60 ° C and 90% RH. The peeling state of the board | substrate was observed, and (circle) and no peeling were evaluated as (x).

15) peel strength

A 0.7 mm thick alkali-free glass (thickness; 0.7 mm) having a width of 25 mm and a length of 50 mm and an acrylic plate having a thickness of 2 mm were bonded to have a resin thickness of 25 μm, and cured at 3000 mJ using an 157 mW ultra-high pressure mercury lamp. The tensile adhesive strength at the time of testing this test piece at the speed of 5 mm / min using the tensile tester was measured.

(Measurement of physical properties of sheet-shaped cured product and preparation of test sample)

The test sample for the sheet or film-shaped cured product was prepared by the method described in Examples 21 to 32. The test method of a sheet-shaped hardened | cured material is shown below.

16) pencil hardness

According to JIS K 5400, the pencil hardness of the film was measured using the pencil scratch tester. That is, on the PET film which has a hard-coat layer (15 micrometers in thickness), the pencil was scratched about 5 mm by applying the load of 1 kg from the top at an angle of 45 degrees, and confirmed the grade of a scratch. It measured five times and the pencil hardness below 1 rank which showed the occurrence of 2 or more scratches among 5 times was described as a pencil hardness test result.

17) Scratch Resistance Test

200g / cm <2> was put on steel wool # 0000, and 200 reciprocation was carried out, and the state of a flaw was confirmed using the stereomicroscope and compared with the limit sample of 5 steps. Evaluation 5 means no scratch, evaluation 1 means scratch occurrence, and evaluation 4 ~ 2 means that the degree of scratch is in the middle.

18) adhesion

According to JIS K 5400, 100 checkerboard scales were made by inserting 11 longitudinal and horizontal cut lines at 1 mm intervals on the surface of the film. After the cellophane tape was brought into close contact with the surface, the number of mass grids remaining without being peeled off at one time was indicated.

19) bendability

The coated sheet was carried out by bending the UV coated surface to 180 degrees outward.

A: It is bent without abnormality in appearance.

B: Gold or peeling occurs on the coating film surface.

C: Substrate cracking occurs.

20) Translucency

After application | coating hardening on the board | substrate, in order to determine the transparency of a film | membrane, the state of cloudy etc. was visually determined.

A: very transparent

B: There is transparency

C: cloudy

Synthesis Example 1

3.2 mol (926.5 ml) of dimethyloltricyclodecane diacrylate, 8.0 mol (1814.1 ml) of isobornyl methacrylate, 4.8 mol (645.5 ml) of 2-hydroxypropyl methacrylate, 2,4-diphenyl-4 4.8 mol (1145.9 ml) of methyl-1-pentene and 2400 ml of toluene were introduced into a 10.0 L reactor, and 240 mmol of benzoyl peroxide was added at 90 캜 to react for 6 hours. After the polymerization reaction was stopped by cooling, the reaction mixture was poured into a large amount of hexane at room temperature to precipitate a polymer. The obtained polymer was washed with hexane, filtered off, dried and weighed to obtain 1392.6 g of Copolymer A (yield: 40.5 wt%).

Mw of the obtained copolymer A was 8950, Mn was 3470, and Mw / Mn was 2.58. By carrying out ¹³ C-NMR, ¹ H-NMR analysis and elemental analysis, copolymer A totaled 18.2 mol% of structural units derived from dimethyloltricyclodecane diacrylate, and 51.1 of structural units derived from isobornyl methacrylate. 30.7 mol% of structural units derived from mol% and 2-hydroxypropyl methacrylate were contained. Moreover, the terminal group of the structure derived from 2, 4- diphenyl-4-methyl-1- pentene is dimethylol tricyclodecane diacrylate, isobornyl methacrylate, 2-hydroxypropyl methacrylate, and 2, 4- 8.3 mol% existed with respect to the total amount of diphenyl-4-methyl-1-pentene. Moreover, the ratio of pendant acrylate was 12.10 mol%.

Copolymer A is soluble in toluene, xylene, THF, dichloroethane, dichloromethane and chloroform, and no gel formation was recognized. In addition, the cast film of copolymer A was a transparent film without cloudiness.

&Lt; Synthesis Example 2 &

4.8 mole (950.4 g) of 1,4-butanediol diacrylate, 6.4 mole (922.7 g) of dicyclopentanyl methacrylate, 4.8 mole (692.2 g) of 2-hydroxypropyl methacrylate, 2,4-diphenyl- 4.8 mol (1135 g) of 4-methyl-1-pentene and 2400 ml of toluene were introduced into a 10.0 L reactor, and 240 mmol of benzoyl peroxide was added at 90 ° C to react for 6 hours. After the polymerization reaction was stopped by cooling, the reaction mixture was poured into a large amount of hexane at room temperature to precipitate a polymer. The obtained polymer was washed with hexane, filtered off, dried and weighed to obtain Copolymer B.

Mw of the obtained copolymer B was 12500, Mn was 3640 and Mw / Mn was 3.43. ^{By performing 13} C-NMR, ¹ H-NMR analysis and elemental analysis, copolymer B totaled 27.8 mol% of structural units derived from 1,4-butanediol diacrylate and the total of structural units derived from dicyclopentanyl methacrylate. 27.8 mol% and 41.6 mol% of structural units derived from 2-hydroxypropyl methacrylate were contained. In addition, the terminal groups of the structure derived from 2,4-diphenyl-4-methyl-1-pentene are 1,4-butanediol diacrylate, dicyclopentanyl methacrylate, 2-hydroxypropyl methacrylate, and 2,4. 10.1 mol% was exist with respect to the total amount of -diphenyl-4-methyl-1-pentene. Moreover, the ratio of pendant acrylate was 20.4 mol%.

Copolymer B is soluble in toluene, xylene, THF, dichloroethane, dichloromethane and chloroform, and no gel formation was recognized. In addition, the cast film of copolymer B was a transparent film without cloudiness.

&Lt; Synthesis Example 3 &

5 mol (990 g) of 1,4-butanediol diacrylate, 1 mol (144.2 g) of dicyclopentanyl methacrylate, 4 mol (576.8 g) of 2-hydroxypropyl methacrylate, 2,4-diphenyl-4 5 mol (1182 g) of methyl-1-pentene and 2400 ml of toluene were introduced into a 10.0 L reactor, and 240 mmol of benzoyl peroxide was added at 90 ° C to react for 6 hours. After the polymerization reaction was stopped by cooling, the reaction mixture was poured into a large amount of hexane at room temperature to precipitate a polymer. The obtained polymer was washed with hexane, filtered off, dried and weighed to obtain Copolymer C.

Mw of the obtained copolymer C was 9230, Mn was 3210 and Mw / Mn was 2.88. ^{By performing 13} C-NMR, ¹ H-NMR analysis and elemental analysis, copolymer C totaled 45.6 mol% of structural units derived from 1,4-butanediol diacrylate and the structural units derived from dicyclopentanyl methacrylate. 12.3 mol% and 42.1 mol% of structural units derived from 2-hydroxypropyl methacrylate were contained. In addition, the terminal groups of the structure derived from 2,4-diphenyl-4-methyl-1-pentene are 1,4-butanediol diacrylate, dicyclopentanyl methacrylate, 2-hydroxypropyl methacrylate, and 2,4. 14.6 mol% was present relative to the total amount of -diphenyl-4-methyl-1-pentene. Moreover, the ratio of pendant acrylate was 32.6 mol%.

Copolymer C is soluble in toluene, xylene, THF, dichloroethane, dichloromethane and chloroform, and no gel formation was recognized. In addition, the cast film of copolymer C was a transparent film without cloudiness.

<Synthesis Examples 4-15 and Synthesis Examples 16-20>

By using the same method as in Synthesis Example 1, various copolymers were synthesized by changing the type and amount of acrylate used in the formulations shown in Tables 1-2. On the other hand, Synthesis Examples 16-20 are synthesis examples for comparison. The results are collectively shown in Tables 1-2.

<Examples 1-20 and Comparative Examples 1-8>

Various copolymers synthesize | combined by the synthesis example and the additives, such as (meth) acrylates and a polymerization initiator, were mixed by the ratio shown to Tables 3 and 4, and the curable composition was obtained. Next, this curable resin composition was cured according to the above various test methods, and performance evaluation was performed. The performance evaluation results are shown in Tables 3 and 4.

<Examples 21 to 26 and Comparative Examples 9 and 10>

The component shown in Table 5 was mix | blended (number is a weight part), and the curable resin composition as a hard coat material was obtained. Next, this curable resin composition was applied to a sheet of untreated polycarbonate (Mitsubishi Engineering Plastics: Iupilon Sheet NF-2000, sheet thickness of 1.00 mm) using a spin coater, and then subjected to peeling treatment on the coated surface. After bonding PET protective film (thickness: 38 micrometers), ultraviolet-ray was irradiated at the distance of 10 cm of high pressure mercury lamp of 120 W / cm in air atmosphere, and the sheet which has a hard-coat layer (thickness 10-15 micrometers) was obtained. Next, the hard coat layer (cured product) was evaluated for performance according to the above various test methods. Table 5 also shows the results of the performance evaluation.

<Examples 27-32 and Comparative Examples 11, 12>

The component shown in Table 6 was mix | blended (number is a weight part), and the curable resin composition as a clear coating material was obtained. Next, this curable resin composition was applied to a sheet of untreated polycarbonate (Mitsubishi Engineering Plastics: Euphilon Sheet NF-2000, sheet thickness of 1.00 mm) using a spin coater, and a protective film made of PET with a peeling treatment on the coated surface. After bonding (thickness: 38 micrometers), the ultraviolet-ray was irradiated at a distance of 10 cm of a high pressure mercury lamp of 120 W / cm in air atmosphere, and the sheet which has a clear coat layer (thickness 10-15 micrometers) was obtained. Next, the clear coat layer (cured product) was evaluated for performance according to the above various test methods. Table 6 also shows the results of the performance evaluation.

Explanation of symbols in the table

IBOMA; Isobonyl methacrylate

DCPM; Dicyclopentanyl methacrylate

DCPA; Dicyclopentanylacrylate

HOP; 2-hydroxypropyl methacrylate

HO; 2-hydroxyethyl methacrylate

CD570; Ethoxylated 2-hydroxyethyl methacrylate

DMTCD; Dimethyloltricyclodecane diacrylate

14BDDA; 1,4-butanediol diacrylate

MMA; Methyl methacrylate

DCP-A; Tricyclodecane dimethanol diacrylate (Kyoeisha Kagaku Co., Ltd. product)

1.9ND; 1,9-nonanediol dimethacrylate (produced by Kyoeisha Kagaku Co., Ltd.)

FA-513M; Dicyclopentanyl methacrylate (made by Hitachi Kasei Co., Ltd.)

FA-513AS; Dicyclopentanyl acrylate (made by Hitachi Kasei Co., Ltd.)

TMP; Trimethylolpropane trimethacrylate (produced by Kyoeisha Kagaku Co., Ltd.)

TMP-A; Trimethylolpropane triacrylate (manufactured by Kyoeisha Chemical Co., Ltd.)

AO-60; Adeka Staff AO-60 (Adeka Products: Antioxidant)

Perbutyl O; t-butylperoxy-2-ethylhexanate (made by Nippon Oil Industries, Ltd.)

Irgacure 184; 1-hydroxycyclohexyl-phenyl-ketone (product of Chiba-Specialty-Chemicals company)

SR-833S; Tricyclodecane dimethanol diacrylate (product of Satomer company)

SR-349; EO modified bisphenol A diacrylate (Sartomer Co., Ltd. product)

SR-348; EO modified bisphenol A dimethacrylate (Sartomer Co., Ltd. product)

EBECRYL 8405; Urethane acrylate / 1,6-hexanedioldiacrylate = 80/20 (product made by Daicel Cytec Co., Ltd.)

EBECRYL 8402; Urethane acrylate (made by Daicel Cytec Co., Ltd.)

DPHA; Dipentaerythritol hexaacrylate (made by Daicel Cytec Co., Ltd.)

SR-285; Tetrahydrofurfuryl acrylate (Sartomer company)

PhEA; Phenoxyethyl acrylate

Irgacure 819; Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (manufactured by BASF Corporation)

In Tables 1-2, the number of component (a)-(c) shows the usage amount (mol), the number in parentheses is mole% in acrylates, the number of DMP shows the usage amount (mol), and in parenthesis The numbers are mole% relative to the total amount of acrylates. On the other hand, when MMA is used as the other monomer component, it is calculated as acrylates. Moreover, content of each component is an abundance ratio (mol%) of the structural unit derived from each component which exists in a copolymer, Computed by said Formula (1)-(5), respectively. When MMA is used as the other monomer component, this is calculated as a structural unit derived from acrylates.

Claims (16)

(A) component: Monofunctional (meth) acrylic acid ester (a) which has alicyclic structure, Monofunctional (meth) acrylic acid ester (b) which has an alcoholic hydroxyl group, bifunctional (meth) acrylic acid ester (c), 2, As a copolymer obtained by copolymerizing the component containing 4-diphenyl-4-methyl-1- pentene (d), it has a reactive (meth) acrylate group derived from bifunctional (meth) acrylic acid ester (c) in a side chain, It is a copolymer which has a structural unit derived from 2, 4- diphenyl-4-methyl-1- pentene (d) at the terminal, has a weight average molecular weight of 2000-50000, and also toluene, xylene, tetrahydrofuran, dichloroethane, or Soluble polyfunctional (meth) acrylic acid ester copolymer soluble in chloroform, and
(B) component: The monomer which has one or more functional groups which have a polymerizable unsaturated double bond,
As a resin composition which uses as an essential component, the compounding quantity of (A) component with respect to the sum total of (A) component and (B) component is 1-70 wt%, and the compounding quantity of (B) component is 99-30 wt%, characterized by the above-mentioned. Curable resin composition. The method of claim 1,
The weight average molecular weight (Mw _A ) of (A) component is 6000-50000, (B) component is an oligomer, the weight average molecular weight (Mw _B ) is 6000 or less, Mw _A -Mw _B is 1000 or more, It is characterized by the above-mentioned. Curable resin composition. The method of claim 1,
Curable resin composition whose (B) component is a monomer whose molecular weight which has 1 or more of functional groups which have a polymerizable unsaturated double bond is 1000 or less. The method of claim 1,
Curable resin composition characterized by the compounding quantity of 10-70 wt% and (B) component of 90-30 wt% with respect to the sum total of (A) component and (B) component. The method of claim 1,
Soluble polyfunctionality which is 0.02-0.35 as molar fraction (M _d ) represented by following formula (1) that the introduction amount of 2, 4- diphenyl-4-methyl-1- pentene (d) in the said (A) component is represented. It is a (meth) acrylic acid ester copolymer, Curable resin composition characterized by the above-mentioned.
M _d = (d) / [(a) + (b) + (c) + (d)] (1)
Here (a), (b), (c) and (d) are a monofunctional (meth) acrylic acid ester which has a structural unit derived from the monofunctional (meth) acrylic acid ester (a) which has an alicyclic structure, and an alcoholic hydroxyl group ( The number of moles of the structural unit derived from b), the structural unit derived from the bifunctional (meth) acrylic acid ester (c), and the structural unit derived from 2,4-diphenyl-4-methyl-1-pentene (d) Indicates. The method of claim 1,
Introduced amount into the side chain of the reactive (meth) acrylate group derived from the bifunctional (meth) acrylic acid ester (c) in the said (A) component is 0.05? As molar fraction ( _Mc1 ) represented by following formula (2). Curable resin composition characterized by the above-mentioned.
M _c1 = (c1) / [(a) + (b) + (c)] (2)
(C1) shows the number-of-moles of the structural unit (c1) which contains a bifunctional (meth) acrylate group in a side chain here. The method of claim 1,
Wherein (A) is introduced amount of the monofunctional (meth) acrylate (b) having an alcoholic hydroxyl group, to a mole fraction represented by the formula _{(3) (M b) 0.05} ? 0.60 soluble polyfunctional (meth) as in component Curable resin composition characterized by the acrylic ester copolymer.
M _b = (b) / [(a) + (b) + (c)] (3) The method of claim 1,
Wherein (A) the mole fraction represented by the monofunctional (meth) to the introduced amount of the acrylate ester (a), formula (4) having an alicyclic structure in the component (M _a) as 0.05? 0.60 soluble polyfunctional (meth Curable resin composition characterized by the above-mentioned.
M _a = (a) / [(a) + (b) + (c)] (4) The method of claim 1,
Monofunctional (meth) acrylic acid ester (a) which has the said alicyclic structure is isobornyl methacrylate, isobonyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, dicyclopentenyl acrylate, dicyclophene At least one alicyclic group selected from the group consisting of tenyloxyethyl acrylate, dicyclopentanyl acrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentenyloxyethyl methacrylate, and dicyclopentanyl methacrylate It is monofunctional (meth) acrylic acid ester which has a structure, The curable resin composition characterized by the above-mentioned. The method of claim 1,
The group which the monofunctional (meth) acrylic acid ester (b) which has the said alcoholic hydroxyl group consists of 2-hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate, and the partially ethoxylated 2-hydroxy methacrylate. It is monofunctional (meth) acrylic acid ester chosen from curable resin composition characterized by the above-mentioned. The method of claim 1,
The said bifunctional (meth) acrylic acid ester (c) is 1, 4- butanediol diacrylate, 1, 6- hexanediol diacrylate, 1, 9- nonane diol diacrylate, and dimethylol tricyclodecane diacrylate. It is 1 or more types of bifunctional (meth) acrylic acid ester chosen from the group which consists of curable resin compositions characterized by the above-mentioned. The method of claim 1,
The monomer which has one or more functional groups which have a polymerizable unsaturated double bond of the said B component is 1 or more types of (meth) acrylic acid chosen from monofunctional (meth) acrylic acid ester and bifunctional (meth) acrylic acid ester which have an alicyclic structure. Curable resin composition characterized by the above-mentioned. The method of claim 1,
Furthermore, curable resin composition containing a photoinitiator as (C) component. It is obtained by hardening | curing curable resin composition of any one of Claims 1-13, The hardened | cured material characterized by the above-mentioned. It is formed from the hardened | cured material of Claim 14, The optical material characterized by the above-mentioned. 16. The method of claim 15,
An optical material, characterized in that the optical material is an optical plastic lens or prism.