TW201223980A - Curable resin composition and cured product thereof - Google Patents

Abstract

The objective of the present invention lies in providing a multifunctional (meth)acrylate composition, which has the excellent optical properties such as low color dispersion, high light transmittance, etc. and the excellent miscellaneous property balances required by an optical lens and a prism material, without causing refractivity divergence while maintaining the high optical property even under a severe practical use condition such as a humid and hot condition. The solution of the present invention is a curable resin composition, which is a resin composition consisting of ingredient (A) and ingredient (B). The ingredient (A) is a copolymer containing the polymerizable group obtained from the copolymerization of ingredients containing (a) mono-functional (meth)acrylate containing an alicyclic structure, (b) mono-functional (meth)acrylate containing an alcoholic hydroxyl group, (c) bifunctional (meth)acrylate, and (d) 2,4-diphenyl-4-methyl-1-pentene, while the ingredient (B) is a monomer with the functional group containing one or more unsaturated double bond. The blending amount of the ingredient (A) is 1 to 70 wt%.

Description

201223980 VI. Description of the Invention: [Technical Field] The present invention relates to an actual use condition which is excellent in optical characteristics, heat resistance and processability such as low color dispersion and high light transmittance, and in severe heat and humidity conditions. A curable resin composition having improved optical properties, low water absorption, and adhesion to an inorganic material, and a cured product thereof. [Prior Art] Many monomers having a reactive unsaturated bond are cleaved by an unsaturated bond, and a polymer can be produced by selecting a catalyst in which a chain reaction occurs and an appropriate reaction condition. In general, since the types of monomers having an unsaturated bond are extremely diverse, the richness of the type of the obtained resin is also remarkable. However, a monomer having a high molecular weight molecular weight of 10,000 or more which is generally referred to as a polymer compound is relatively small. For example, ethylene, substituted ethylene, propylene, substituted propylene, styrene, alkylstyrene, alkoxystyrene, norbornene, various acrylates, butadiene, cyclopentadiene, dicyclopentane Alkene, isoprene, maleic anhydride, maleic imide, fumarate, allyl compound and the like are representative monomers. These monomers can be synthesized individually or by copolymerization to form a wide variety of resins. The use of these resins is mainly limited to the field of relatively inexpensive livelihood machines, and is hardly applicable to the field of advanced technologies requiring high heat resistance, size, or micro-machining in the field of optical and electronic materials. The reason for this is that the polymer which is usually synthesized from the above monomers is thermoplastic, and in order to satisfy the mechanical properties, a large number of high molecular weight bodies are required, so

S 201223980 Characteristics required in cutting-edge technology such as heat resistance or micro-machining. On the other hand, the curable resin composition is suitably used as a material for mechanical parts, an electric appliance, an electronic component material, an automobile part material, a civil construction material, a molding material, and the like, and can also be used as a material for a coating or an adhesive. In addition, when combined with an inorganic substrate to form a mixed member, not only the coefficient of thermal expansion is lowered, but also the refractive index of the inorganic substance and the resin can be adjusted, and the appearance of the resin composition and the cured product thereof can be controlled to exhibit transparency. It is therefore particularly suitable as a material in electrical or electronic parts or optical applications. For example, the digital camera module is being mounted on a mobile phone and is being miniaturized, and is also required to be reduced in cost. Further, the demand for a car camera for a novel use or a bar code reader for a home buyer is increased. When it is used for such applications, it is required to have high heat resistance such as long-term heat resistance and low water absorption, in addition to the heat resistance of the soldering at the time of manufacture, and the temperature exposure in the summer in actual use. As a method for solving the disadvantages of such a vinyl-based thermoplastic polymer, Patent Documents 1 to 3 disclose a polymer having a (meth)methacryloyl group or a vinyl ether group in a pendant. For example, Patent Document No. discloses a (meth)methacryl fluorenyl side group-type polymer obtained by cationically polymerizing a heterogeneous polymerizable monomer such as 2-vinyloxyethyl acrylate (VEA) and photopolymerization. A photosensitive composition formed by an initiator. Further, Patent Document 2 discloses a photosensitive composition comprising a (meth)methacryloyl group-based polymer, a compound having a photoreactive unsaturated carboxyl group, and a photopolymerization initiator. Further, Patent Document 3 discloses a heteropolymerizable monomer such as 2-vinyloxyethyl acrylate (VEA), which has an inactive photoreactive unsaturated carboxylate in its own cationic polymerization 201223980. In the solvent compound, a method of producing a polymer solution is obtained by performing a homopolymerization or a copolymerization using a cationic polymerization catalyst. However, according to the technique of using a heterogeneous polymerizable monomer disclosed in these documents, when a reactive polymer produced is used, a low water absorption property which is required in the field of advanced optical lens and enamel is not obtained, A polymer and a curable resin composition having improved properties such as moldability, heat resistance, and high transparency, and optical properties under excellent practical use conditions such as damp heat conditions, and adhesion to inorganic materials. On the other hand, Patent Document 4 discloses that a monovinyl aromatic compound and a bifunctional (meth) acrylate are copolymerized, and have a reactivity derived from a bifunctional (meth) acrylate in a side chain (methyl group). A soluble polyfunctional vinyl aromatic copolymer of structural units of acrylate groups. However, the soluble polyfunctional vinyl aromatic copolymer obtained by the technique disclosed in this document has excellent heat decomposition resistance to high temperature heat warp, and has a reactive (meth) acrylate group in a side chain, and is processability. It is excellent in solvent solubility, but it cannot be used in optical lenses for low-color dispersion applications. It is limited in practical use and is a material that does not improve adhesion to inorganic materials. Further, Patent Document 5 discloses a composition characterized in that it contains 1 to 25% by weight of a linear aliphatic divalent alcohol having 4 to 8 carbon atoms in a methyl methacrylate (MMA) slurry. The bis(meth) acrylate is used as a constituent component. Moreover, the manufacture of the MMA-based slurry composition disclosed in this document is disclosed, which is a combination of MMA, or MMA, and a vinyl copolymerizable therewith.

S 201223980 Polymer and chain transfer agent are subjected to normal temperature or heat polymerization in the presence of a polymerization initiator in an inert gas (e.g., n2 gas) atmosphere. Further, as a specific example of the chain transfer agent in this document, only sulfur compounds such as lauryl mercaptan, octyl thioglycolate, toluene thiophenol, naphtholthiol 'benzyl mercaptan, etc., regarding 2, 4-di Phenyl-4-methyl-1-pentene (hereinafter also referred to as DMP) is not specifically disclosed. Further, it is not suggested that the refraction at the time of moist heat can be multiplied by coexistence of a structural unit having a monofunctional (meth) acrylate (a) having a terminal group derived from DMP and an alicyclic structure of an alicyclic structure. The rate of disagreement occurred. Moreover, the composition obtained by the technique disclosed in the literature does not improve the adhesion to inorganic materials under severe practical use conditions such as moist heat conditions. Further, Patent Document 6 discloses a polymerizable composition composed of a vinyl monomer and a di(meth)acrylate compound, and also discloses the use of DMP, but the amount thereof is used as a decimal point of a usual chain transfer agent. The use of '% of the product is also cross-linked gelation, and does not show solvent solubility. Further, Patent Document 7 discloses a thermosetting resin composition for color filters, which is characterized by self-hardening. a copolymer and an organic solvent, the self-curable copolymer containing (1) an epoxy group-containing (meth) acrylate, (2) a hydroxyl group-containing (meth) acrylate, and (3) (methyl) a constituent unit composed of acrylic acid and (4) an aromatic group-containing (meth) acrylate. Moreover, 'self-hardening copolymers obtained by the techniques disclosed in this document 'for achieving a desired molecular weight range in the polymerization stage' may be used, mercaptopropionic acid 'mercaptopropionate, thioglycol, thioglycerol, twelve

-8- S 201223980 A well-known molecular weight regulator such as a base thiol or an α-methyl styrene dimer. However, in the technique disclosed in this document, since only a vinyl compound having two or more functional groups having a plurality of vinyl groups is not added at the time of polymerization, only one or less terminal derived from a molecular weight modifier can be introduced into the polymer chain. The function of having a function from the terminal group gives the disadvantage of insufficient formation. Further, in this document, the self-curable copolymer obtained by the disclosed technique forms a thermosetting resin composition in a resin composition with an epoxy resin, but with the acrylate resin, The hardening reaction does not occur, and there is a disadvantage that the strength and heat resistance of the resin composition to be blended are lowered. Therefore, it has excellent optical characteristics such as low color dispersion and high light transmittance, and has a balance of characteristics such as low water absorption, moldability, and heat resistance, and optical characteristics under low practical conditions such as damp heat conditions. A curable resin composition having improved water absorbability, heat resistance, and adhesion to an inorganic material has not been present. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Patent Publication No. Sho. [Patent Document 5] Japanese Laid-Open Patent Publication No. JP-A No. Hei. No. Hei. No. 2002-121228.

C 201223980 [Patent Document 7] JP-A-2009-1 770. SUMMARY OF THE INVENTION [Problem to be Solved by the Invention] An object of the present invention is to provide a curable resin composition which has low color dispersion, high light transmittance, and the like. Excellent optical properties, in the advanced technology fields such as low water absorption, processability, heat resistance, etc., the balance of various characteristics required for optical lens and tantalum materials is excellent, and it is improved under the severe practical conditions such as damp heat conditions. Optical properties and adhesion to inorganic materials. [Means for Solving the Problem] The present invention relates to a curable resin composition which is a resin composition containing (A) component and (B) component as essential components, and (A) component: a single article having an alicyclic structure Functional (meth) acrylate (a), monofunctional (methyl) propionate (b) with an alcoholic hydroxyl group, bifunctional (meth) acrylate ((〇 and 2,4-diphenyl-) a copolymer obtained by copolymerizing a component of 4-methyl-1-pentene (d) and having a reactive (meth)acrylic acid derived from a bifunctional (meth) acrylate (c) in a side chain Ester group, copolymer having a structural unit derived from 2,4-diphenyl-4-methyl-pentene (d) at the end, having a weight average molecular weight of 2 〇〇〇 to 50000' and more soluble in toluene Soluble polyfunctional (meth) acrylate copolymer of xylene, tetrahydrofuran, dichloroethane or chloroform; (B) Component: one or more officials with polymerizable unsaturated double bonds

-10- S 201223980 The monomer of the energy base; the blending amount of the component (A) is 1 to 70% by weight based on the total of the components (A) and (B), and the blending amount of the component (B) is 99~3 0 wt %. The amount of introduction of 2,4-diphenyl-4-methyl-1-pentene (d) in the component (A) is represented by a molar fraction Md represented by the following formula (1), preferably 0.02 to 0.35, and the amount of introduction of the reactive (meth) acrylate group from the bifunctional (meth) acrylate (c) to the side chain is represented by the molar fraction Mel represented by the following formula (2). It is preferably 0.05 to 0.5. In addition, the amount of introduction of the monofunctional (meth) acrylate (b) having an alcoholic hydroxyl group in the component (A) is represented by a molar fraction Mb represented by the following formula (3), preferably 0.05 to 〜 The amount of introduction of the monofunctional (meth) acrylate (a) having an alicyclic structure is 0.60, and is expressed by the molar fraction of the following formula (4), preferably 0.05 to 0.60.

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

Mci=(cl) /[(a) + (b) + (c) ] (2)

Mb=(b) /[(a) + (b) + (c) ] (3)

Ma=(a) /[(a) + (b) + (c) ] (4) Here, (a), (b), (c) and (d) represent monofunctional from alicyclic structures The structural unit of (meth) acrylate (a)' is a structural unit derived from a monofunctional (meth) acrylate (b) having an alcoholic hydroxyl group, a structural unit derived from a bifunctional (meth) acrylate (c), And the molar number of the structural unit derived from 2,4-diphenyl-4-methyl-1-pentene (d). Further, (cl) means that a bifunctional (meth)propionate is contained in the side chain.

S -11 - 201223980 The molar number of the structural unit. The monofunctional (meth) acrylate (a) having an alicyclic structure is preferably selected from the group consisting of isobornyl methacrylate, isobornyl acrylate, cyclohexyl methacrylate, and cyclohexyl acrylate. , dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, dicyclopentanyl acrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentenyloxyethyl methacrylate, and One or more monofunctional (meth) acrylates having an alicyclic structure in the group formed by dicyclopentyl acrylate. The monofunctional (meth) acrylate (b) having an alcoholic hydroxyl group is preferably selected from the group consisting of 2-hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate, and partially ethoxylated. A monofunctional (meth) acrylate in a group of 2-hydroxy methacrylate. The bifunctional (meth) acrylate (c) is preferably selected from the group consisting of 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, and 1,9-nonanediol. One or more bifunctional (meth) acrylates in the group of diacrylate and dimethylol tricyclodecane diacrylate. The monomer or oligomer having one or more functional groups having a polymerizable unsaturated double bond as the component B is preferably a monofunctional (meth) acrylate having an alicyclic structure and 2 More than one (meth) acrylate selected from functional (meth) acrylates. The curable resin composition of the present invention preferably further contains a photopolymerization initiator as the component (C). Further, the present invention is a cured product obtained by curing the curable resin composition. Furthermore, the present invention is an optical material,

-12- S 201223980 is formed by the above hardened material. As the optical material, an optical plastic lens or a crucible is preferable. Advantageous Effects of Invention According to the present invention, it is possible to provide a curable resin composition which has excellent optical characteristics such as low color dispersion and high light transmittance, and is advanced in advanced technical fields such as low water absorption, workability, and heat resistance. The optical lens has excellent balance of various characteristics required for the ruthenium material, and improves optical properties and adhesion to inorganic materials under severe practical use conditions such as damp heat conditions. [Embodiment] [Mode for Carrying Out the Invention] The curable resin composition of the present invention will be described in detail. The soluble polyfunctional (meth) acrylate copolymer (hereinafter also referred to as a copolymer) of the component (A) of the present invention contains a monofunctional (meth) acrylate (a) having an alicyclic structure and has an alcohol Monofunctional (meth) acrylate (b) and bifunctional (meth) acrylate (hydroxyl monomer, and 2,4-diphenyl-4-methyl-1-pentene (d) a copolymer obtained by copolymerization and having a reactive (meth) acrylate group derived from a bifunctional (meth) acrylate (c) in a side chain, and having 2, 4 at the end a soluble polyfunctional (meth) acrylate copolymer of the structural unit of diphenyl-4-methyl-1.pentene (d). Here, the so-called soluble means that it is soluble in toluene and xylene. Tetrahydrofuran, dichloro

S -13- 201223980 In ethane or chloroform. The soluble test was carried out under the conditions shown in the synthesis examples. Further, it is understood that the monofunctional (meth) acrylate means that the number of ethylenic double bonds present in the molecule is one, and the bifunctional (meth) acrylate means that the number of ethylenic double bonds present in the molecule is Two, polyfunctional (meth) acrylate copolymers mean that the number of ethylenic double bonds present in a molecule is two or more. Further, a monofunctional (meth) acrylate having an alicyclic structure (a) is also referred to as a component (a), and a monofunctional (meth) acrylate having an alcoholic hydroxyl group (b) is also referred to as a component (b). The bifunctional (meth) acrylate (c) is also referred to as component (c), and the 2,4-diphenyl-4-methyl-1-pentene (d) is also referred to as component (d) or DMP. Since the copolymer is obtained by copolymerizing a monofunctional (meth) acrylate and a bifunctional (meth) acrylate, it has a branched structure or a crosslinked structure, but the amount of the structure is limited to exhibit solubility. degree. Therefore, it is a copolymer having a structural unit (cl) containing an unreacted (meth)acrylic group derived from a bifunctional (meth) acrylate (c) in a side chain. This unreacted (meth)acrylic group is referred to as a pendant (meth)acrylic group, and since it exhibits polymerizability, it can be polymerized by a further polymerization treatment to give a solvent-insoluble resin cured product. Further, the copolymer has a structural unit derived from the component (d) at the terminal. By introducing this structural unit at the end of the copolymer, it is possible to obtain a cured product having improved moldability such as mold release property. 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). Here, in the structural unit from the component (c), two (

-14- 201223980 Both of the polymerizable double bonds (referred to as vinyl groups) contained in the methyl acrylate have a structural unit (c2) which participates in polymerization to form a branched structure or a crosslinked structure, and contains only 1 The vinyl groups are involved in the polymerization, and the other vinyl groups do not react and remain unreacted (meth)acrylic-based structural units (cl). The DMP of the component (d) has a chain transfer agent and prevents the increase in molecular weight and is present at the end of the copolymer. The amount of the component (d) to be introduced into the copolymer is represented by the molar fraction Md represented by the following formula (n), which is 0_02 to 0.35, preferably 〇.〇3 to 0.30, and particularly preferably 〇·〇5 to 0.15. .

Md=(d) /[(a) + (b) + (c) + (d) ] (1) where ' (a), (b), (c) and (d) are from (a), The number of moles of the structural unit of each component of (b), (c) and (d). The mold release property and the low water absorbability can be improved by introducing a structural unit derived from the component (d) in the above range at the end of the copolymer. The bifunctional (meth) acrylate (c) causes branching or cross-linking of the copolymer, and at the same time, the pendant vinyl group gives the copolymer which is hardenable and exhibits heat resistance upon hardening, so that it is important as a crosslinking component. task. As the bifunctional (meth) acrylate, cyclohexane dimethanol diacrylate, dimethylol tricyclodecane diacrylate, cyclohexane dimethanol dimethacrylate, dimethylol tricyclohexane can be used. Decane dimethacrylate, ethylene glycol diacrylate, propylene glycol diacrylate, 1,4-butanediol diacrylate, hexanediol diacrylate, diethylene glycol diacrylate, ethylene glycol diacrylate Ester, propylene glycol diacrylate, 丨/- butanediol dimethacrylate, hexanediol dimethacrylate, diethylene glycol dimethacrylate

S -15- 201223980 A bifunctional (meth) acrylate such as an ester, but is not limited thereto. As a suitable specific example of the bifunctional (meth) acrylate, cyclohexane dimethanol diacrylate and dihydroxyl group are preferably used from the viewpoint of the easiness of the polymerization control and the heat resistance of the obtained polymer. Tricyclodecane diacrylate. The copolymer has a structural unit (ci) containing a reactive (meth) acrylate group derived from a bifunctional (meth) acrylate (c) in a side chain, but a structural unit (cl) represented by the formula (2) The molar fraction ^«^ may be 0.05 or more and 0.5 or less, preferably 0 · 1 to 〇.

Mci-(cl) /[(a) + (b) + (c) ] ( 2 ) Here, (cl) in the formula represents a structural unit (cl) containing a (meth) acrylate group. number. By satisfying the above molar fraction, it is possible to obtain a molded article which is excellent in light or heat hardenability and excellent in heat resistance and mechanical properties after curing. The structural unit derived from the bifunctional (meth) acrylate (c) may contain structural units (c 1 ) and other structural units, but from all the bifunctional (meth) acrylates (c) containing these The molar fraction Mc of the structural unit (c) may be 〇.1 to 〇.7, preferably 0.15 to 0.65.

Mc-(cl) /[(a) + (b) + (c) ] (5). In order to improve solvent solubility, low water absorption, heat resistance, optical properties, and processability of the copolymer, a monofunctional (meth) acrylate (a) having an alicyclic structure is important. As such a monofunctional (meth) acrylate having an alicyclic structure, it is selected from isobornyl methacrylate, isobornyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, -16-

S 201223980 Dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, dicyclopentanyl acrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentenyloxyethyl methacrylate, A One or more monofunctional (meth) acrylates having an alicyclic structure in the group formed by dicyclopentyl acrylate are not limited thereto. By introducing the structural unit derived from these components into the copolymer having an alicyclic structure, not only the gelation of the polymer can be prevented, the solubility in the solvent can be improved, and the low color dispersion of the copolymer can be improved. Optical properties such as properties, low water absorption, and heat resistance. The monofunctional (meth) acrylate (a) having an alicyclic structure is preferably a compound represented by the following formula (al). ARC-( R')n ( a 1 ) Here, A is a (meth)acryloxy group, R is a single bond or an alkylene or polyalkylene oxide having a carbon number of 1 to 1 Å, and a C-based fat. A family ring, R' is an alkyl group having 1 to 10 carbon atoms substituted by an aliphatic ring, and η is 0 to 5. The other preferable monofunctional (meth) acrylate (a) having an alicyclic structure is a compound represented by the following formula (a2). R1 Ο CH2 = CC-〇-(- R3Ofv R2 (a2) Here, R1 represents a hydrogen atom or a methyl group 'r2 represents a hydrocarbon group having an alicyclic structure having a carbon number of 6 to 15, and R3 represents a carbon number. The alkylene group of 2 to 4 represents an integer of 〇10. As a suitable specific example, it is selected from the viewpoint of cost, gelation prevention, and moldability of the obtained polymer. Acrylic

S -17- 201223980 borneol ester, acesulfame isobornyl ester, cyclohexyl methacrylate, cyclohexyl acrylate, dicyclopentenyl propyl storage, dicyclopentenyloxyethyl acrylate, and acrylic acid One or more of the group consisting of cyclopentyl ester, dicyclopentenyloxyethyl methacrylate, dicyclopentaoxyethyl methacrylate, and dicyclopentanyl methacrylate having an alicyclic structure Monofunctional (meth) acrylate. In order to improve the adhesion of the copolymer to an inorganic material under severe practical conditions such as damp heat conditions, a monofunctional (meth)acrylic acid vinegar (b) having an alcoholic hydroxyl group is important. Examples of such a monofunctional (meth) acrylate having an alcoholic hydroxyl group include 2-hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate, and 3-hydroxypropyl (meth)acrylate. 4-hydroxybutyl methacrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate and partially ethoxylated 2-hydroxy methacrylate, preferably 2-hydroxyethyl methacrylate. These (meth) acrylate-based mono-systems having an alcoholic hydroxyl group may be used singly or in combination of two or more kinds. The monofunctional (meth) acrylate (b) having an alcoholic hydroxyl group is preferably a compound represented by the following formula (b1). [Chemical 2] R1 Ο CH2 = C - C - Ο - R4 (bl) Here, 'R1 represents a hydrogen atom or a methyl group, and R4 represents a hydrocarbon group having a hydroxyl group of 2 to 6 carbon atoms. a monofunctional (meth) acrylate (b) containing an alcoholic hydroxyl group, a molar fraction of (a) component, (b) component, and (c) component in the copolymer, and a monofunctional group derived from an alcoholic hydroxyl group The molar fraction of the structural unit of (meth) acrylate (c), and Mb represented by formula (3) may be 0.05

-18- S 201223980 is 0.60 or less, preferably 0.1 to 0.3.

Mb= ( 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 satisfying the above molar fraction, it is possible to obtain a copolymer which is excellent in the optical properties under severe practical conditions such as moist heat conditions and in good adhesion to inorganic materials. Further, Ma represented by the above formula (4) may be 0.05 or more and 0.60 or less, preferably 0.1 to 0.3. DMP has the function as a chain transfer agent to control the molecular weight of the copolymer. The molecular weight of the copolymer is expressed by the weight average molecular weight Mw, and is in the range of 2,000 to 50,000, preferably in the range of 3,000 to 25,000. Further, the range of Mw of 6 000 to 500 00 is good for the relationship with the component (B). The formability and mold release property of the cured resin are improved by using a relatively low molecular weight copolymer. Further, as the component (e) for improving the solvent solubility and processability of the copolymer, a monofunctional (meth) acrylate having no alicyclic structure and a hydroxyl group can be added. Examples of such (meth) acrylate include methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-methylhexyl acrylate, and 2-ethyl acrylate. The hexyl hexyl ester, octyl acrylate or the like is preferably methyl methacrylate or n-butyl acrylate. These (meth) acrylate-based single systems may be used singly or in combination of two or more kinds, but are preferably selected from the group consisting of methyl methacrylate, methyl acrylate, and n-butyl acrylate. Above (A

S -19- 201223980 based) acrylate. Further, 'the other structure derived from the monomer component (e) is less than 30 m for the structural unit derived from the monomer component (a), the structural unit derived from the single j, and the structural unit derived from the monomer component (c). Within the range of %, β is 'soluble from other points of view. The methyl ester copolymer may contain 20 to 35 mol% of the structural unit derived from the component (a) and the structural unit derived from the component (b). The structural unit of 55 to 10 mol%, preferably 50 to 12 m to 40 to 15 mol%, and the structural unit derived from the component (d). The structure derived from the bifunctional (meth) acrylate (c) In the case of a single mole %, the heat resistance of the cured product is insufficient, and when the amount is more than 55 mol%, the moldability is lowered, and the molded article is lowered. Further, other structural orders derived from the monomer (e) component The structural unit derived from the component (a) and the total amount of the component (b) may be in a range of less than 30 mol%. The method for producing the copolymer used as the component (A) is not limited, and DMP, 2 is used. Monofunctional acrylate aryl and bifunctional (meth) acrylates adjusted to the desired level It is produced by a method of using a radical polymerization initiator and a solvent at 20 to 200 ° C, for example, by a stripping method, precipitation in a weak solvent, etc. This copolymer is for the above solvent l〇〇g 'With the unit, the total amount of the phase component (b), can be based on) Acrylic acid 5 5 5 mol%, from (c) component P %, more preferably 2 to 3 5 mol % Bit if not up to 10 The strength of this structural sheet is significant, and there is no special fragrance compound relative to the structural unit. If necessary, the temperature is usually dissolved by using lg or more.

-20- S 201223980 Solubility. It is preferred to dissolve 5 g or more with respect to the above-mentioned solvent 100 g at 25 °C. Next, the component (B) will be explained. As the component (B), a monomer having one or more functional groups having a polymerizable unsaturated double bond is used. Here, the monomer as the component (B) may be an oligomer, but is not the same as the copolymer of the component (A). Further, the term "different" means that it does not contain a monofunctional (meth) acrylate having an alicyclic structure (a), a monofunctional (meth) acrylate having an alcoholic hydroxyl group (b), or a bifunctional group. A copolymer obtained by copolymerizing a component of (meth) acrylate (c) and 2,4-diphenyl-4-methyl-1-pentene (d). Further, the oligomer may be a homopolymer or a copolymer, and may be a low molecular weight polymer having a molecular weight (Mw) of 1 0000 or less, preferably 6,000 or less, more preferably 5,000 or less, and still more preferably 1,000 or less. the following. Further, the monomer as the component (B) may be a compound having no molecular weight distribution, and in this case, a plurality of compounds may be used. A monomer having a molecular weight of 1,000 or less is preferred. When the monomer is an oligomer, the above molecular weight means Mw. Further, in the relationship with the component (A), the relationship between the molecular weight Mw of the monomer of the component (B) and the Mw of the copolymer of the component (A) may be lower than, more preferably lower than 1 〇〇〇. . The above-mentioned single system has one or more functional groups having a polymerizable unsaturated double bond, and a functional group having a polymerizable unsaturated double bond includes a vinyl group, a (meth)methacrylinyl group or the like. The monomer as the component (B) is preferably a (meth) acrylate monomer. When the (meth) acrylate single system has one or more (meth) methacryl fluorenyl groups in the molecule, one type or two or more types may be used. As such

S-21 - 201223980 (B) The (meth) acrylate used in the component (B) is used in combination with the component (A) without reducing the hardenability, and the viscosity of the composition can be adjusted, and the heat resistance is multiplied. At the same time, optical characteristics such as low color dispersion and high light transmittance are improved. Further, physical properties such as hardness and flexibility of the cured product can be improved. The (meth) acrylate single system may have a molecular weight of 6,000 or less, preferably 5,000 or less, particularly preferably less than 1,000. Further, it may be a monomer (oligomer) having a molecular weight distribution such as polyethylene glycol di(meth)acrylate, and the Mw at this time may be 6,000 or less, preferably 5,000 or less, more preferably 2,000 or less. , especially good for 1 〇〇〇 or less. Advantageously, the monomer or mixture thereof is formed from a compound having no molecular weight distribution. The (meth) acrylate monomer may be a copolymerizable with the component (A). For example, it is preferably a (meth) acrylate having an alicyclic structure, and particularly preferably a monofunctional, bifunctional or trisole. The functional (meth) acrylate is more preferably a monofunctional (meth) acrylate. Further, the (meth) acrylate monomer as the component B is preferably an aliphatic acrylate of C4 to 20, and may have one to three unsaturated bonds derived from an acrylate. The (meth) acrylate having an alicyclic structure is excellent in compatibility with the component (A), and is effectively multiplied by the component (A) to improve the low water absorption, heat resistance, and optical properties of the entire composition. Processability. Further, the urethane-modified (meth) acrylate or ethylene oxide-modified (meth) acrylate type has an effect of improving the softness of the cured product. Further, in order to improve the hardness of the cured product, the (meth)acrylate single system having three or more functional groups has an effect. As the (meth) acrylate monomer, for example, an acrylonitrile group is exemplified.

S 201223980 porphyrin, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, poly Propylene glycol mono(meth)acrylate, cyclohexane-1,4-dimethanol mono(meth)acrylate, tetrahydrofurfuryl (meth)acrylate, phenoxyethyl (meth)acrylate, (a) Phenyl polyethoxylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, o-phenylphenol mono(ethoxy)acrylate, o-phenylphenol (meth)acrylate Polyethoxylate, p-cumylphenoxyethyl (meth)acrylate, isobornyl (meth)acrylate, tribromophenoxyethyl (meth)acrylate, bicyclo(meth)acrylate Amyl ester, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol Di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, tricyclodecane dimethanol (meth) acrylate, bisphenol A polyethoxylate Di(meth)acrylate (for example, Lut-349, 8-foot-348, manufactured by Sartomer Co., Ltd.), bisphenol octapolypropoxy di(meth)acrylate, bisphenol F polyethoxy di(methyl) Acrylate, ethylene glycol di(meth)acrylate, trimethylolpropane triethoxyacetate (meth)acrylate, tris(2-hydroxyethyl)isocyanate tris(methyl) Acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylic acid_, polyethyl alcohol-(meth)acrylic acid vinegar (for example, @SR-344, SR-268, etc. by Sartomer Co., Ltd.), Tris(propylene methoxyethyl) isomeric cyanurate, pentaerythritol tetra(meth) acrylate, dipentaerythritol hexa(meth) acrylate, dipentaerythritol penta (meth) acrylate, tripentaerythritol hexa Acetate vinegar, tripentaerythritol penta(methyl) propylene vinegar phthalate -23- 201223980, thiol trimethylacetate neopentyl glycol di(meth) acrylate, hydroxytrimethyl acetic acid neopentyl Di(meth)acrylic acid of ε_caprolactone adduct of alcohol (for example, 曰本化药(股) KAYARAD ΗΧ-220, ΗΧ-620, etc.), trimethoprim tris(meth) acrylate, trimethylolpropane polyethoxy tri(meth) acrylate, ditrimethylolpropane tetra ( A monomer such as a methyl propyl acrylate or a urethane modified (meth) acrylate (for example, EBACRYL 8405 manufactured by Daicel Scientific Co., Ltd., EBACRYL 8402, etc.). Particularly preferred are 6-hexanediol di(meth)acrylic acid vinegar, dimethylolpropane tri(meth)acrylate, trimethylolpropane trioxyethyl (meth)acrylate, Pentaerythritol tris(meth)acrylic acid vinegar, dipentaerythritol hexa(meth) acrylate, amine urethane modified (meth) acrylate, bisphenol A polyethoxy di(meth) acrylate, ethylene Alcohol di(meth)acrylate. The curable resin composition of the present invention may contain a polymerization initiator as the component (C), and is preferably a photopolymerization initiator. The curable resin composition of the present invention can be molded and cured by thermal polymerization. However, when an optical material such as a lens is molded and cured, photohardening which can be controlled by a strict shape is advantageous. Therefore, it is preferred to add a photopolymerization initiator. . Examples of the photopolymerization initiator of the component (C) include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether. Affinity; acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichlorobenzene Ketone, 2-hydroxy is called 2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-l-[4-(methylthio) Phenyl]-2-morpholinylpropane--24-

S 201223980 1-ketones such as ketones; anthraquinones such as 2-ethylhydrazine, 2-tert-butylindole, 2-chloroindole, 2-pentyl onion, etc.; 2,4 - Thioxanthone such as diethylthioxanthone, 2-isopropylthioxanthone or 2-chlorothioxanthone; ketal such as acetophenone dimethyl ketal or benzyl dimethyl ketal a diphenyl ketone such as diphenyl ketone, 4-benzylidene-4'-methyldiphenyl sulfide or 4,4'-bismethylaminodiphenyl ketone; 2, 4, a phosphine oxide such as 6-trimethylbenzimidyl diphenylphosphine oxide or bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide, etc. Used alone or in combination of two or more kinds, more preferably with tertiary amines such as triethanolamine or methyldiethanolamine, ethyl hydrazine, hydrazine-dimethylaminobenzoic acid, hydrazine, hydrazine-dimethylaminobenzoic acid An accelerator or the like of a benzate derivative such as isoamyl ester or the like is used in combination. The curable resin composition of the present invention contains the above-mentioned (A) component and (B) component as essential components, and the content ratio thereof is such that the blending amount of the component (B) below is relative to (A) component and (B). The total amount of the components to be blended is 99 to 30 parts by weight, preferably 90 to 30 parts by weight, more preferably 60 to 45 parts by weight. In addition, when the component (C) is contained, the blending amount of the component (C) is 0.1 to 10 parts by weight based on 100 parts by weight of the total of the blending amount of the component (B) and the component (A). Preferably, it is from 1. 0 to 5 parts by weight. From another viewpoint, each of the curable resin composition may contain (A) component: 1 to 69 wt%, (B) component: 30 to 98 wt ° / 〇, and (C) component: 0 · 1~ 1 Owt%. More preferably, it is (A) component: 25-60 weight%, (B) component: 39-74 weight%, and (C) component: 1-5 weight%. By

S -25-201223980 The blending ratio of the component (A), the component (B) and the component (C) is within the above range, and the moldability observed in mold release property or hardenability is multiplied, and A balance of properties of heat resistance and optical properties. Further, when the amount of the component (C) is too small, the curing is likely to be insufficient, and the heat resistance and the light resistance are lowered. When the amount is too large, the mechanical strength is lowered and the heat resistance is lowered. Further, when the organic solvent and the mash are contained in the curable resin composition, the above content is calculated by excluding the above. Further, in the curable resin composition of the present invention, a polymerization inhibitor, an antioxidant, a mold release agent, a photosensitizer, an organic solvent, a decane coupling agent may be added to the curable resin composition of the present invention as needed. , leveling agent, antifoaming agent, antistatic agent, and UV absorber, light stabilizer, inorganic, organic various materials, anti-fungal agents, antibacterial agents, etc., and give their respective functions. The curable resin composition of the present invention can be obtained by mixing the above-mentioned (A) component (B) component and (C) component and optionally other components in an arbitrary order. The curable resin composition of the present invention is stable over time. The curable resin composition of the present invention can be obtained by irradiating an active energy ray such as ultraviolet rays. Here, when the active energy ray is irradiated and hardened, 'specific examples of the light source to be used include a xenon lamp, a carbon arc, a germicidal lamp, a fluorescent lamp for ultraviolet light, a high pressure mercury lamp for photocopying, a medium pressure mercury lamp, a high pressure mercury lamp, and super. High-pressure mercury lamps, electrodeless lamps, metal halide lamps' or scanning type, curtain type electron beam acceleration road electron beams. Moreover, when the curable resin composition of the present invention is cured by ultraviolet irradiation, it is hard.

-26- S 201223980 The amount of ultraviolet radiation required for chemical conversion can be about 300 to 20,000 mJ/cm2. Further, in order to sufficiently cure the resin composition, it is preferred to irradiate an active energy ray such as ultraviolet rays in an inert gas atmosphere such as nitrogen. Further, the curable resin composition of the present invention may optionally employ a decane coupling agent, a polymerization inhibitor, a leveling agent, a surface lubricant, an antifoaming agent, a photostabilizer, an antioxidant, a plasticizer, an antistatic agent, An additive such as a chelating agent or a solvent. The cured product of the curable resin composition of the present invention can be obtained by irradiating an active energy ray such as an ultraviolet ray or a visible light laser according to a usual method. When ultraviolet rays are used, they are irradiated with a low-pressure or high-pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a xenon lamp, or the like. In particular, as the light source, a lamp having a high energy intensity of 350 to 450 nm is preferable. The refractive index of the cured product of the curable resin composition of the present invention obtained by irradiating an active energy ray such as ultraviolet rays is preferably 1.49 or more at 25 ° C, and more preferably 1.51 or more at 25 C. In particular, when a tantalum lens sheet is produced from the resin composition for an optical material of the present invention, if the refractive index of the cured product is less than 1.49' at 25 °C, there is a problem that sufficient front luminance cannot be ensured. Further, the Abbe number of the cured product (the number 物质 which is a property of the substance which changes the refractive index due to the wavelength of light) is preferably 40.0 or more, and more preferably 50_0 or more. If the Abbe number of the cured product is less than 40.0, it is not preferable because of chromatic aberration and color bleeding. The cured resin obtained by molding and curing the curable resin composition of the present invention is excellent as an optical material such as a 稜鏡' lens. Particularly suitable as a 稜鏡 lens sheet, a Fresnel lens, a lenticular lens, a spectacle lens,

S -27- 201223980 Materials for optical plastic lenses such as aspherical lenses. Moreover, such a lens system can be advantageously used in an image pickup apparatus. Further, the curable resin composition or the cured resin may be used in a photonic-oriented application such as a compact disc, an optical fiber, or an optical waveguide, a printing ink, a paint, a clear paint, a lacquer, a hard coat, or the like. Further, the cured product of the curable resin composition of the present invention may be used as an adhesive layer, and examples of the article having such an adhesive layer include a mobile phone, a portable game machine, a digital camera, and the like. When the polarizing film and the protective sheet are bonded to each other by using the curable resin composition of the present invention, for example, it is not limited to a protective sheet made of an alkali-free glass or quartz glass which is excellent in active energy ray permeability, and even a large absorbing ultraviolet ray is used. A protective sheet such as a force plate or a polycarbonate can be used because of the good reaction hardenability of the composition. The curable resin composition of the present invention can be used as a coating device such as a roll coater, a spin coater or a screen printing method on a substrate such as a polarizing film, and the film thickness of the adhesive is 1 to 100 μm. The coating is applied to the protective sheet, and ultraviolet rays are irradiated from the upper side of the protective sheet to be hardened, and then proceed. [Examples] Hereinafter, the present invention will be described by way of Examples, but the present invention is not limited thereto. Furthermore, the parts in each case are all parts by weight. Further, in the measurement of each physical property in the examples, sample preparation and measurement were carried out by the method described below.

-28- S 201223980 (1) Molecular Weight and Molecular Weight Distribution of Polymer The molecular weight and molecular weight distribution of the soluble polyfunctional (meth) acrylate copolymer were determined by using GPC (manufactured by Tosoh Corporation, HLC-8120GPC) in solvent: tetrahydrofuran ( THF), flow rate: 1.0 ml/min, column temperature: 40 °C. The molecular weight of the copolymer was measured using a calibration curve of monodisperse polystyrene as a molecular weight in terms of polystyrene. (2) Structure of polymer The JNM-LA600 type nuclear magnetic resonance spectroscopic device manufactured by JEOL Ltd. was determined by 13C-NMR and 1H-NMR analysis and halogen analysis. The resonance line of tetramethylnonane was used as an internal standard using chloroform_dl as a solvent. (3) Solubility test For 100 ml of various organic solvents (toluene, xylene, tetrahydrofuran, dichloroethane, and chloroform) at 25 ° C, a copolymer lg was added, and the mixture was stirred for 30 minutes using a magnetic stirrer, and the solubility was visually confirmed. All of the above organic solvents were dissolved, and no solubility was observed when the gel was formed: 〇. (4) The test piece for physical property measurement was prepared by opening a gap of 〇·2~1 _〇mm between two glass plates having a width of 50 mm, a length of 50 mm, and a thickness of 1.0 mm, and being wound around the outer periphery by a polyimide tape. In the glass mold, a curable composition is injected, and one side of the glass mold is irradiated with ultraviolet rays for 5 seconds by the high-pressure mercury lamp, and then the glass mold is applied.

S -29- 201223980 was placed in an inert gas oven under a nitrogen stream and hardened by heating at 180 ° C for 1 hour. The hardened resin sheet was released from the glass mold and used for various physical properties. (5) Measurement of refractive index The refractive index and Abbe number of 589 nm were measured by an Abbe refractometer (manufactured by ATAGO Co., Ltd.). (6) Hue (YI); a flat panel of thickness i.〇mm was measured with a color difference meter (Tokyo Electric Co., Ltd. MODEL TC-8600), showing YI値(7) haze (turbidity) and total light The transmittance was 0.2 mm thick, and the haze (turbidity) and total light transmittance of the sample were measured using an integrating sphere type light transmittance measuring apparatus (SZ-Σ90 manufactured by Nippon Denshoku Co., Ltd.). (8) Mold release property: It was evaluated by the ease of releasing the hardened resin from the mold. 〇· · ·. Good mold release from the mold △ · · ·. The mold release system is slightly difficult X · · · · Demoulding is difficult or mold residue (9) Die reproducibility: Observe the surface shape of the hardened resin layer

-30- 201223980 Surface shape with mold. 〇 · · · · Reproducibility is good △ ····The conditions for curing (light, heat) are good reproducibility X .... Reproducibility (10) Burr, leakage: by removing the hardened resin from the mold In the mold, the size of the burrs generated outside the product part of the molded product and the degree of leakage of the resin into the gap of the mold are evaluated. The amount of burrs generated is less than 0.05 mm, and the resin leaks into the mold gap. 1. 〇mm. △ . . . • The amount of burrs generated is 〇.〇5mm or more and less than 22mm. The resin leaked into the mold gap system of 1.0 mm or more and did not reach 3,0 mm. X · ·.. The amount of burrs generated is 〇.2 mm or more, and the resin shallow leak enters the die gap to be 3.0 mm or more. (1 1 ) Reflow heat resistance: A 1 mm thick flat plate was used as a sample, and a spectral transmittance of 400 nm was measured by a spectrophotometer CM-3700d (manufactured by Konica-Minolta Co., Ltd.). The measurement timing was carried out at 180 ° C for 60 minutes after post-curing heat resistance test and after heat resistance test at 260 ° C for 8 minutes in an air oven. (1 2 ) Water absorption rate A 1 mm thick flat plate was used as a sample, and the weight of a sample which was vacuum dried at 60 ° C for 24 hours was taken as W 〇 to be measured to a level of ± 〇 1 m g

S -31 - 201223980 Weigh it and humidify it for 1 week in a constant temperature and humidity chamber at a temperature of 85 ° C and a relative humidity of 85 %. After humidification, the moisture adhering to the sample is blown off, and the sample can be weighed to a scale of ± 〇. The water absorption rate was calculated by the following formula. Prepare three identical samples and test them in the same way.

Wo/Wxl00 = water absorption rate (1 3 ) heat-resistant cyclicity using an ultra-high pressure mercury lamp of 157 mW, with an alkali-free glass (thickness: 〇.7 mm) and a 2 mm-thick acrylic plate at a thickness of 25 μm at an energy of 3000 mJ The sample was subjected to one cycle of one cycle, -35 ° C for 30 minutes, and 85 ° C for 30 minutes, and the peeling appearance of the two substrates was observed, and no peeling was evaluated as 〇, and peeling was evaluated as X. (14) Moisture resistance Using a 157 mW ultrahigh pressure mercury lamp, the sample of the alkali-free glass (thickness: 〇.7 mm) and the 2 mm thick acryl plate at a thickness of 25 μm was observed at 60° with an energy of 3000 mJ. C. The peeling appearance of the two substrates after being left for 1 hour under 90% RH was evaluated as no peeling, and peeling was evaluated as X. (1 5 ) Peeling strength An alkali-free glass (thickness: 0_7 mm) having a width of 25 mm and a length of 50 mm and a length of 50 mm and a thickness of 2 mm were laminated to a thickness of 25 μm.

S 201223980 Acrylic sheet, hardened with an energy of 3〇〇〇mj using a 157mW ultra-high pressure mercury lamp. For this test piece, the tensile strength at the time of the test at a rate of 5 mm/min was measured using a tensile tester. (Measurement of physical properties of sheet-like cured product and test sample) Samples for test of sheet or film-like cured product were prepared by the methods described in Examples 21 to 32. The test method for the sheet-like cured product is shown below. 0 (1 6 ) Pencil hardness The pencil hardness of the film was measured in accordance with JIS K 5400 using a pencil scratch tester. Namely, on a PET film having a hard coat layer (thickness: 15 Pm), the pencil was scratched by a load of lkg at an angle of 45 degrees, and the scratch was observed to be about 5 mm. The pencil hardness at the level of 1 at which the damage was observed twice or more in 5 times was described as the result of the stray hardness test. (1 7) The scratch resistance test was carried out on steel wool #〇〇〇〇, and a load of 200 g/cm2 was applied 'reciprocated 2 times, and the condition of the damage was confirmed using a stereoscopic microscope, by comparison with the sample of the 5-stage limit. determination. Evaluation of 5 means no damage. Evaluation 1 means that damage occurred, and evaluation of 4 to 2 means that the degree of damage was in the middle. (1 8) Adhesion

S -33- 201223980 In accordance with JIS K 54〇0, slits of 11 vertical and horizontal are introduced at intervals of 1 mm on the surface of the film to make one checkerboard. Indicates the number of squares that remain without peeling off when the cellophane tape is applied to the surface. (1) Bending property The coated sheet was formed by bending the UV coated surface to the outside and bending it to 180 degrees. A: There is no abnormality in appearance and it is bent. B: Cracking or peeling occurred on the surface of the coating film. C: Cracking occurred in each substrate. (20) Transparent appearance After coating and hardening on a substrate, it is judged by a state in which the visibility is blurred, in order to determine the transparency of the film. A: a very transparent feeling is obtained, B: has a transparent feeling, C: blur is not synthesized. Example 1 monomethylol tricyclodecane diacrylate 3·2 mol (926 5 ml), isobornyl methacrylate 8 〇莫耳(18141ml), bishydroxypropyl methacrylate 4.8 mole (645.5ml), 2,4_diphenyl_4_methyl-丨-pentene 4·8 mole (1 145.9ml 2400 ml of toluene was placed in a reactor of l〇_〇L, and 240 mmol of benzoyl peroxide was added at 9 ° C to carry out a reaction for 6 hours. borrow

-34- S 201223980 After cooling to stop the polymerization reaction, 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, separated by filtration, dried, and weighed to obtain a copolymer of *A 1392.6 g (recovery rate: 40.5 wt%). The obtained copolymer VIII had an Mw of 8,950, a Μη of 3,470, and a Mw/Mn of 2.58. By performing 13C-NMR, W-nmr analysis and elemental analysis, the copolymer A contained a total of 18.2 mol% of structural units derived from dimethylol tricyclodecane diacrylate vinegar, and a total of 51.1 mol% from A The structural unit of isopropyl acrylate vinegar, 30.7 mol% of the structural unit derived from 2-hydroxypropyl methacrylate. Further, the terminal group derived from the structure of 2,4-diphenyl-4-methyl-1-pentene is based on dimethylol tricyclodecane diacrylate, isobornyl methacrylate, The total amount of 2-hydroxypropyl methacrylate and 2,4-diphenyl-4-methyl-1-pentene is present at 8 to 3 mol%. Further, the ratio of the pendant acrylate was 12.10 mol%. The copolymer oxime was soluble in toluene, xylene, THF, dichloroethane, dichloromethane, chloroform, and no gel formation was observed. Further, the cast film of the copolymer A was a film which was transparent without being turbid. Synthesis Example 2 1,4-butanediol diacrylate 4.8 mol (95 0.4 g), dicyclopentanyl methacrylate 6.4 mol (922.7 g), 2-hydroxypropyl methacrylate 4.8 mol ( 692.2 g), 2,4-diphenyl-4-methyl-p-pentene 4.8 mol (1135 g), 2400 ml of toluene were placed in a 10.0 L reactor, and 240 mmol of benzoyl peroxide was added at 90 ° C. The reaction was allowed to proceed for 6 hours. Stop by cooling

S-35-201223980 After the polymerization reaction, 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, separated by filtration, dried, and weighed to obtain a copolymer B. The obtained copolymer B had Mw of 12,500, Μη of 3,640, and Mw/Mn of 3.43. By 13 C-NMR, h-NMR analysis and elemental analysis, the copolymer B contained a total of 27.8 mol% of a structural unit derived from i,4-butanediol diacrylate, and a total of 27.8 mol. /〇 The structural unit derived from dicyclopentanyl methacrylate, 41.6 mol% of the structural unit derived from 2-hydroxypropyl methacrylate. Further, the terminal group 'from the structure of 2,4-diphenyl-4-methyl-1-pentene is relative to 1,4-butanediol diacrylate, dicyclopentanyl methacrylate, methyl The total amount of 2-hydroxypropyl acrylate and 2,4-diphenyl-4-methyl-1.pentene was present at 10% by mole. Further, the ratio of the pendant acrylate was 2 0.4 mol%. The copolymer B was soluble in toluene, xylene, THF, dichloroethane, dichloromethane, and chloroform, and no gel formation was observed. Further, the cast film of the copolymer B was a film which was transparent without being turbid. Synthesis Example 3 1,4-butanediol diacrylate 5 mol (99 g), methyl acrylate-cyclopentyl ester 1 mol (144.2 g) 2-methylpropyl propyl propionate 4mol (576.8g), 2,4-phenyl-4-methyl-1-pentaphene 5 molar (Ii82g), 2400ml of toluene into the reactor of l〇.OL, add 24 at 9〇t 〇mm〇1 of benzophenone peroxide was allowed to react for 6 hours. After cooling to stop the polymerization reaction, the reaction mixture is poured into a large amount of hexane at room temperature to cause precipitation polymerization.

S -36- 201223980. The obtained polymer was washed with hexane, separated by filtration, dried, and weighed to obtain a copolymer C. The obtained copolymer C had Mw of 9230, Μη of 3210, and Mw/Mn of 2.88. By performing 13C-NMH, h-NMR analysis and elemental analysis, the copolymer C system contained a total of 45.6 mol% of a structural unit derived from fluorene, 4-butanediol diacrylate, and a total of 12.3 mol% of methyl group. The structural unit of dicyclopentanyl acrylate, 42.1 mol% of the structural unit derived from 2-hydroxypropyl methacrylate. Further, 'the terminal group derived from the structure of 2,4-diphenyl-4-methyl-pentene is relative to 1,4-butanediol diacrylate, dicyclopentanyl methacrylate, methacrylic acid The total amount of 2-hydroxypropyl ester and 2,4-diphenyl-4-methyl-1-pentene was present at 14.6 mol%. Further, the ratio of the pendant acrylate was 3 2.6 mol%. The copolymer C was soluble in toluene, xylene, THF, dichloroethane, dichloromethane, and chloroform, and no gel formation was observed. Further, the cast film of the copolymer c was a film which was transparent without being turbid. Synthesis Examples 4 to 15 and Synthesis Examples 16 to 20 In the same manner as in Synthesis Example 1, the types and amounts of acrylates were changed by blending as shown in Tables 1 to 2 to synthesize various copolymers. Further, Synthesis Examples 16 to 20 are comparative examples for comparison. The results are summarized in Tables 1 and 2. Examples 1 to 20 and Comparative Examples 1 to 8 Various copolymers synthesized in the synthesis examples were synthesized in the ratios shown in Tables 3 and 4.

S-37-201223980 A mixture of an additive such as a (meth) acrylate or a polymerization initiator to obtain a curable composition. Next, the curable resin composition was cured by the above various test methods to evaluate the performance. The performance evaluation results are shown in Tables 3 and 4. Examples 21 to 26 and Comparative Examples 9 and 10 The components shown in Table 5 were blended (numbers are parts by weight) to obtain a curable resin composition as a hard coating material. Next, the curable resin composition was applied onto a sheet of untreated polycarbonate (made of Mitsubishi Engineering Plastics: Iupilon Sheet NF-2000, sheet thickness of 1.5 mm) using a spin coater, and was coated. After bonding the PET protective film (thickness: 38 μm) which had been subjected to the release treatment, it was irradiated with ultraviolet light at a distance of 10 cm in a high-pressure mercury lamp of 120 W/cm in an air atmosphere to obtain a hard coat layer (thickness 10 to 15). A thin sheet of μιη). Next, the performance of the hard coat layer (hardened product) was evaluated by the above various test methods. The results of the combined performance evaluation are shown in Table 5. Examples 27 to 32 and Comparative Examples 11 and 12 The components shown in Table 6 were blended (numbers are parts by weight) to obtain a curable resin composition as a transparent coating material. Next, the curable resin composition was applied to a sheet of untreated polycarbonate (made of Mitsubishi Engineering Plastics: Iupilon Sheet NF-2000, sheet thickness 1.00 mm) using a spin coater, and the coated surface was subjected to coating. After peeling off the PET protective film (thickness: 38μηι), it is a 120W/cm high-pressure mercury lamp in an air environment, -38-

S 201223980 Irradiated ultraviolet rays at a distance of 10 cm to obtain a sheet having a clear coat layer (thickness J 〜 15 15 μm). Next, the performance of the transparent coating (cured material) was evaluated by the above various test methods. The results of the combined performance evaluation are shown in Table 6. Description of the symbols in the table ΙΒΟΜΑ: isobornyl methacrylate DCPM: dicyclopentanyl methacrylate DCPA: dicyclopentyl acrylate HOP: 2-hydroxypropyl methacrylate HO: 2-hydroxyethyl methacrylate CD570: Ethoxylated 2-hydroxyethyl methacrylate DMTCD: Dimethylol tricyclodecane diacrylate 14BDDA : 1,4-butanediol diacrylate MMA: Methyl methacrylate DCP-A : Tricyclodecane dimethanol diacrylate (manufactured by Kyoeisha Chemical Co., Ltd.) 1,9ND : 1,9-nonanediol dimethacrylate (manufactured by Kyoeisha Chemical Co., Ltd.) FA-513M: methyl Dicyclopentyl acrylate (manufactured by Hitachi Chemical Co., Ltd.) FA-513AS: Dicyclopentyl acrylate (manufactured by Toray Chemical Industry Co., Ltd.) TMP: Trimethylolpropane trimethacrylate (Kyoeisha Chemical Co., Ltd.) system)

S-39-201223980 ΤΜΡ-Α : Trimethylolpropane triacrylate (manufactured by Kyoeisha Chemical Co., Ltd.) AO-60: Adekastub ΑΟ-60 (manufactured by Adeka: Antioxidant)

Perbutyl 0: tert-butylperoxy-2-ethylhexanoate (manufactured by Nippon Oil & Fats Co., Ltd.)

Irgacure 184: 1-hydroxy-cyclohexyl-phenyl-ketone, (manufactured by Ciba Specialty Chemicals Co., Ltd.) SR-833 S: Tricyclodecane dimethanol diacrylate (manufactured by Sartomer Co., Ltd.) SR-349 : EO modified double Phenol A diacrylate (manufactured by Sartomer Co., Ltd.) SR-348 : EO-modified bisphenol a dimethacrylate (Sart〇iner & Ses) EBECRYL 84〇5: urethane acrylate/1,6 _Hexanediol diacrylate = 80/20 (manufactured by Daicel Scientific Co., Ltd.) 'EBECRYL 8 402: Ethyl urethane acrylate (manufactured by Sigma Scientific Co., Ltd.) DPHA · Pentaerythritol hexaacrylate (Daicel Science) "manufactured by the company" 'SR-285: tetrahydrofurfuryl acrylate (manufactured by Sart Co., Ltd.)

PhEA: phenoxy acetoacetate hgacure 819: bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide (manufactured by BASF Corporation) 201223980 Tables 1 to 2, component (a)~ The number in (c) indicates the amount of use (mole), the number in the digital acrylates in the brackets is the number of the M'% of the DMP, and the number in parentheses indicates the total relative to the acrylate. Mohr in terms of quantity. /. . Further, when MMA is used as the other monomer component, this is calculated as an acrylate. Further, the content of each component is calculated from the above formulas (1) to (5) by the existence ratio (mol%) of the structural unit derived from each component present in the copolymer. Further, when MMA is used as the other monomer component, this is calculated as a structural unit derived from acrylic vinegar.

S -41 - 201223980 rH w 5(50) 2(20) 3(30) 3(23.1) 17100 2480 1 6.90 1 〇m 48.10% 19.60 32.30 10.60 16.70 Ο 5(50) 1(10) 4(40) 4 (40) 14600 3130 4.66 〇m 49.10 9.60 41.30 10.30 22.80 Oi 4(40) 2(20) 4(40) 4(40) 16900 2250 1 7.51 _I 〇璀37.80 19.30 42.90 9.80 23.80 00 w 5(50) 3( 30) 2(20) 2(20) 14700 | 2540 | I 5.79 | 〇m 48.60 29.10 22.30 3.70 13.20 〇 1(10) 4(40) 5(50) 5(50) i 13900 3340 丨 4.16 | 〇m 9.00 38.20 53.60 8.40 26.30 CO 6.4(40) 4.8(30) | 4.8(30) 4.8(30) 10800 3230 3.34 〇m 39.40 27.40 33.20 7.90 13.60 1C 1(10) 3(30) 6(60) 6(60) 19200 2930 | 6.55 | 〇 8.4 8.29 29.30 62.30 14.70 14.70 呀 Q 6.4(40) 4.8(30) 4.8(30) 4.8(30) 15300 3260 4.69 〇m 38.10 29.30 32.60 8.20 15.40 CO ϋ 1(10) 4(40) 5(50) 5(50) 9230 3210 2.88 〇m 12.30 Γ 42.10 45.60 10.20 32.60 Oi CQ 6.4(40) 4.8(30) 4.8(30) 4.8(30) 12500 3640 3.43 〇m 31.60 41.60% 27.80 10.60 20.40 < 8(50) 4.8(30) 3.2(20) 4.8(30) 8950 i 3470 1 2.58 | 〇m 1 51.10 30.70 18.20 8.30 12.10 Synthetic copolymer ΙΒ0ΜΑ DCPM DCPA HOP o CD570 DMTCD 14BDDA i DMP ms chain Mw Mn Mw/Mn m ingot t? Silent gel to produce impurities (%) of each component ΙΒ0ΜΑ DCPM DCPA 1 o CD570 DMTCD 14BDDA 1 DMP side-based acrylic vinegar (cl), a component (6) component 1 other Ί Component fn\ V d 〆 component (b) 1 component 1 other -42- 201223980 s 4.8(30) 3.2(20) 8(50) 4.8(30) 58900 6230 ! 9.45 〇璀28.80 20-90 50.30 7.80 12.40 2 CO 8(50) 4.8(30) 3.2(20) 0.8(5) Gelation 1 Gelation Condensation X 1 j Cannot measure 00 10.4(65) 4.8(30) 0.8(5) 0.8(5) 56800 7720 1 7.36 〇壊64.90 i 29,40 1 5.70 0.87 3.10 at 11.2(70) 4.8(30) 0·8(5) 67200 5340 12.58 〇m 70.20 29.80 1 1.03 CO Oi 8(50) 8(50) 8(50) 3930 I860 1__2^1__1 〇 | | 47.70% | 52.30 12.90 28.30 in o 0.8(5) 12(75) 3.2(20) 4.8(30) 10200 2570 1 3.97 〇4.50 74.20 21.30 5.20 11.70 12(75) 0.8(5) 3.2(20) 4.8(30) 9800 2180 1 4.50 〇m 74.10 4,30 1 21.60 5.10 13.80 co 4(40) 2(20) 4(40 4(40) 16700 2230 __7-49 Π 〇璀39.40 19.30 41.30 ! 10.30 22.70 2 hJ 4(40) 2(20) 4(40) 4(28.6) 1 21300 | 2860 1__7-45 1 39 39 39.10 i 19.80 41 41.10 9.90 23.40 Synthesis Example IBOMA DCPM DCPA CU § s CD570 DMTCD 14BDDA 1 DMP ΙΒ0ΜΑ DCPM DCPA HOP Ο CD570 DMTCD 14BDDA MMA DMP Side-Based Acrylic Vinegar (cl) Copolymer Composition (a) Composition (6) Composition u) 丨Others - Products Physical property Mw Μη Mw/Mn Solvent-soluble 1 gel content of each component (%) Component U) Component (b) Component (C) Other s -43- 201223980 Comparative Example 3 Ο i〇s Η •Η Ο 1 1.526 1 1 50.3 1 I 1.09 1 0.37 1 91.6 1 <1 X 〇89.7 76.1 | 1.35 IXX 0.78 Comparative Example 2 md 94,5 ΙΩ fH Ν rH Ο 1 1.513 1 1 48.0 1 1 1-48 1 1 0.54 1 1 90.2 〇XX 89.3 81.7 1.38 XX 0.30 Comparative Example 1 § ΙΟ (Ν S (Ν rH Ο 1 1.513 ] L 48.7 1 丨 1.52 0.55 1 90.3 XXX 87.8 83.2 1.78 XX 0.58 Example 10 ο ΙΛ ι-Η Ο 1 1.523 1 1 49.8 1 1 1-16 0.36 92.2 〇〇<1 89.1 85.5 0.91 〇〇〇*Example 9 Ο Ο rH <Ν ο 1 1.529 1 1 50.3 1 1.04 0.21 91.8 〇〇〇90.1 86.5 0.72 〇〇 (N CO Example 8 ΙΟ inch § rH <Ν rH Ο 1.522 50.8 1.12 0.26 91.9 〇〇〇89.2 86.2 0.79 〇〇1—< c6 寅Example 7 ο ιί> »-Η (Ν 1—^ Ο 1 1.524 1 1 51.4 1.07 0.24 92.1 〇〇〇89.9 85.3 1.02 〇〇ΙΟ CO Example 6 s LO ΙΑ rH <Ν ι-Η Ο 1 1.524 1 52.2 1.03 0.17 92.3 〇〇<3 89.7 88.1 0.76 〇〇c<i Example 5 &〇CnJ u UD ι-Η (Ν Ο 1 1.525 ! 52.3 1.44 0.32 92.1 〇〇〇88.6 86.5 0.91 〇〇csi Example 4 ΙΟ οι D9 rH Ο 1 1.531 1 1 50.2 1 1.35 0.28 91.8 〇〇〇89.1 87.1 0.82 〇〇c- Example 3 ΙΑ S ΙΟ d 1-Η Ο 1 1.528 1 50.8 1 1.22 0.17 91.7 〇〇〇88.1 86.2 0.86 〇〇CO cd Example 2 ι IG S <Ν — ο 1 1.523 1 1 51.2 1.14 0.32 92.3 〇〇〇88.7 87.6 0.72 〇〇 (N Example 1 1 〇ΙΑ ΙΟ <Ν &lt ;Ν rH c5 1 1,527 1 50.5 1 1.23 0.22 92.1 〇〇〇89.1 87.3 0.67 〇〇00 CO 1 < CQ Ο Q ω DCP-A 1.9ND FA-513M FA-513AS 1 ΤΜΡ-Α Perbutyl 0 Irgacure 184 AO- 60 Physical properties 値 Refractive index (589nm) Abbe number box (%) Full gloss rate (%) Release surface reproducible burr 'leakage 21 Ladder · I |i Heat-resistant fiber after water absorption (%) Sexuality Η 1 1 Copolymer component g Component Ο Other s -44- 201223980 [5 Comparative Example 8 hg § 〇rH CM o 1.492 CO csi in 2.32 1 89.2 XX < CO 00 00 75.3 1.86 〇〇 2.60 Comparative Example 7 (/) s § 〇CSJ d Unable to Pi 1 1 1 1 Comparative Example 6 s 〇d CO ΙΛ LJ9.0 I ! 2.09 | |89·Α ! 〇X 〇88.1 1 _ ____ 1 80.0 1.63 〇ο Εη Comparative example 5 as 〇d u3 1 48.6 | CO CO C4 CN3 1 88.6 1 〇XX CO CO σί 1 1.78 〇X CO ΙΛ Ο Comparative Example 4 〇, g 〇o 1.519 1£> :2.13 1 | 1.53 | 1 89.6 1 〇〇〇88.6 80.3 0. 87 XX 0. 21 Example 20 〇s 〇CN3 o CO CV3 in 48.2 , 1.32 ! 0.48 | σΐ 00 <1 <1 <3 88.3 76.9 2.13 〇〇3.13 Example 19 2 s Guide 〇rH CO o 1.524 | 49.3 | (O 1-H 〇CO s 〇0 <1 89.7 78.6 \ 0.91 〇 〇S rH Example 18 2 s 〇rH CQ fH o 1.528 s' CO Cv3 | 0.36 1 1 92.1 | 〇〇〇89.3 丨84.7 0. 77 〇〇CV3 CO Example 17 s 〇CvJ o | 1.531 | | 52.1 | :1.03 1_ "0.23 | ! 92.6 | 〇〇〇98.1 1 88.2 1 Γ〇·71 COCO Example 16 s 〇N r·^ o 1.498 | 50.3 | CO r»H f 0.19 | | 92.1 | 〇89.7 CO 00 CO rH XX CO Example 15 g 〇CJ o 1 1.526 | CO in ! 1.09 [0.22| | 92.6 | 〇〇〇89.6 86.5 ί 0.65 : 〇〇oi Example 14 g § 〇o rH CO LA CO Csi LO Γ 1.02 1 t-- 〇| 92.5 1 〇〇〇»-Η § "0.73 I 〇〇σ> Example 13 K s 〇Cv3 o 卜 eg tn> fH CsJ iO 1.03 ! 0.21 :92.3 ο 〇〇卜σ 00 86.7 0. 93 〇〇CO CO Example 12 Ο S 〇03 o 1.524 inch | 0.24 | eg 〇> 0 0 〇89.9 CO in 00 "1.20 ; 〇〇 2.8 Example 11 Uh § 〇 CM d CO CSJ LO | 50. 1 1 | 1.23 | "0.33 | oi Oi <1 〇〇89.3 83.2 Ί 〇〇csi Miscellaneous composition (parts by weight) Copolymer DCP-A TMP-A Perbutyl 0 inch 00 1 A0 -60 physical properties 折射率|refractive index (589mn) 丨Abbe number 1 haze (%) 丨 full light hall over rate (%) release surface reproducibility burrs, leakage tl cheeks paste φ 1 water absorption after heat test (%) 丨 heat resistance cycle 1 moisture resistance peel strength (8) (c) component s -45- 201223980 [Table 5]

Example 21 Example 22 Example 23 Example 24 Example 25 Example 26 Comparative Example 9 Comparative Example 10 Copolymer B 1 5 Copolymer D 5 Copolymer Η 10 Copolymer Μ 30 50 55 SR-833S 34 20 20 18 7 EBECRYL8405 18 25 20 EBECRYL8402 30 20 15 10 5 DPHA 27 20 20 30 30 30 50 35 ΤΜΡ-Α 15 27 22 20 17 10 30 5 SR-285 5 3 1 PhEA 3 2 Irgacure819 4.0 3.0 1.5 1.0 1.0 2.0 1.0 Irgacure 184 5.0 2.5 2.0 2.0 2.0 Physical properties 値 3H 3H 3H 3H 2H 2H 3H Η Scratch resistance 5 5 5 5 4 4 5 3 Although 100 100 100 100 100 100 90 100 Bend AAAAAABA [Table 6]

Example 27 Example 28 Example 29 Example 30 Example 31 Example 32 Comparative Example 11 Comparative Example 12 Copolymer B 1 5 Copolymer D 5 Copolymer Η 10 Copolymer Μ 30 50 55 SR-833S 34 20 20 18 7 EBECRYL8405 18 25 20 EBECRYL8402 30 20 15 10 5 DPHA 17 10 10 20 20 20 40 25 ΤΜΡ-Α 15 27 22 20 17 10 30 5 SR-349 10 10 10 10 10 SR-348 10 10 10 SR-285 5 3 1 PhEA 3 2 Irgacure 819 4.0 3.0 1.5 1.0 1.0 2.0 1.0 Irgacure 184 5.0 2.5 2.0 2.0 2.0 Physically compact 100 100 100 100 100 100 90 100 Bend AAAAAABA Transparent look AAAAAABB -46 -

S

Claims (1)

201223980 VII. Patent application garden: 1 · A kind of curable resin composition, which is a resin composition containing (A) component and (B) component as essential components, (A) component: will contain an alicyclic structure Monofunctional (meth) acrylate (a), monofunctional (meth) acrylate having an alcoholic hydroxyl group (b), bifunctional (meth) acrylate (c) and 2,4-diphenyl- a copolymer obtained by copolymerizing a component of 4-methyl-1-pentene (d) and having a reactive (meth) acrylate group derived from a bifunctional (meth) acrylate (c) in a side chain a copolymer having a structural unit derived from 2,4-diphenyl-4-methyl-1-pentene (d) at the terminal, having a weight average molecular weight of from 2,000 to 50,000, more soluble in toluene, xylene, a soluble polyfunctional (meth) acrylate copolymer of tetrahydrofuran, dichloroethane or chloroform; (B) component: a monomer having one or more functional groups having a polymerizable unsaturated double bond; In the total of the components (A) and (B), the blending amount of the component (A) is 1 to 70 wt%/〇, and the blending amount of the component (B) is 99. 3 0 w t%. 2. The curable resin composition of claim 1, wherein the weight average molecular weight (MwA) of the component (A) is from 6000 to 50,000, and the weight average molecular weight (MwB) of the component (B) is an oligomer. Below 6000, and Mwa-Mwb is more than 1,000. 3. The curable resin composition according to claim 1, wherein the component (B) is a monomer having one or more functional groups having a polymerizable unsaturated double bond and having a molecular weight of 1,000 or less. S-47-201223980 4. The curable resin composition of the first aspect of the patent application 'in which the blending amount of the component (A) is 10 to 70 wt% with respect to the total of the components (A) and (B) %, the blending amount of the component (B) is 90 to 30% by weight. 5. The amount of introduction of 2,4-diphenyl-4-methyl-p-pentene (d) in the above-mentioned (A) component, wherein the amount of the curable resin composition of the first aspect of the invention is in the following formula (1) The molar fraction Md shown is a soluble polyfunctional (meth) acrylate copolymer of 〇·〇2 to 0.35; M<j=(d) /[(a) +(b) + (c) +(d) ] (O Here, (a), (b), (c) and (d) represent structural units derived from a monofunctional (meth) acrylate (a) having an alicyclic structure. , a structural unit derived from a monofunctional (meth) acrylate having an alcoholic hydroxyl group (b), a structural unit derived from a bifunctional (meth) acrylate (c), and 2,4-diphenyl-4- The molar number of the structural unit of the methyl-1-pentene (d). 6. The curable resin composition of the first aspect of the invention, wherein the (A) component is derived from the bifunctional (meth)acrylic acid. The amount of introduction of the reactive (meth) acrylate group to the side chain of the ester (c) is represented by the molar fraction Mcl represented by the following formula (2), and is 0.05 to 0.5; Mci = (cl) / [( a)+(b)+(c)] (2) where (c 1 ) is expressed in the side chain The molar composition of the structural unit (cl) of the bifunctional (meth) acrylate group. The sclerosing resin composition of the first aspect of the invention, wherein the (A) component has a single alcoholic hydroxyl group The amount of introduction of the functional (meth) acrylate (b) 'mole fraction Mb shown by the following formula (3) is shown as -48-S 201223980, which is a soluble polyfunctional (meth) acrylate of 0.05 to 0.60. Copolymer; Mb = (b) / [(a) + (b) + (c)] (3) 8. The curable resin composition of claim 1, wherein the component (A) The amount of introduction of the monofunctional (meth) acrylate (a) having an alicyclic structure is represented by a molar fraction Ma represented by the following formula (4) as a soluble polyfunctional (meth)acrylic acid of 0.05 to 0.60. The ester copolymer; Ma = (a) / [(a) + (b) + (c) (4). 9. The curable resin composition of claim 1, wherein the aforementioned alicyclic structure Monofunctional (meth) acrylate (a) is selected from isobornyl methacrylate, isobornyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate Dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, dicyclopentanyl acrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentenyloxyethyl methacrylate, and methyl A monofunctional (meth) acrylate having an alicyclic structure in a group of dicyclopentyl acrylates. The sclerosing resin composition of claim 1, wherein the aforementioned alcohol The monofunctional (meth) acrylate (b) of the hydroxy group is selected from the group consisting of 2-hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate and partially ethoxylated 2-hydroxy methacrylate. A monofunctional (meth) acrylate in a group. 11. The curable resin composition of claim 1, wherein the aforementioned bifunctional (meth) acrylate (C) is selected from the group consisting of 1,4-butanediol S-49-201223980 acrylate, 1, One or more bifunctional (meth) acrylates in the group of 6-hexanediol diacrylate, 1,9-nonanediol diacrylate, and dimethylol tricyclodecane diacrylate. 12. The curable resin composition according to claim 1, wherein the monomer having one or more functional groups having a polymerizable unsaturated double bond in the component B is a monofunctional having an alicyclic structure. One or more (meth) acrylates selected from (meth) acrylate and bifunctional (meth) acrylate. 1 3 The curable resin composition of claim 1, which further contains a photopolymerization initiator as the component (C). A cured product of the invention is characterized in that the curable resin composition according to any one of claims 1 to 13 is cured. An optical material is characterized in that it is formed of a cured product as in item n of the patent application. 16. The optical material of claim i, wherein the optical material is an optical plastic lens or enamel. -50- S 201223980 Four designated representative maps: (1) The representative representative of the case is: No (2) The symbol of the representative figure is simple: No 201223980 5. If there is a chemical formula in this case, please reveal the best indication of the characteristics of the invention. Chemical formula: no-4- S