JP2012188527A - Pseudo-cross-linked curable resin composition, and its copolymer and molded product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a pseudo-cross-linked curable resin composition capable of obtaining a molded product having a sufficient elastic modulus and an excellent elongation at break, its copolymer, and its molded body.SOLUTION: The pseudo-cross-linked curable resin composition contains: a resin A including an urethane bond (pseudo-cross-linked portion) represented by a general formula (1) in a molecule; and a resin B including at least one curable functional group (Y) selected from the group consisting of a vinyl group, an allyl group and a (meth)acryloyl group but not including an urethane group. The mass ratio of the resin A and the resin B (resin A: resin B) is from 10:90 to 90:10. The ratio of the content of the urethane group (X) with respect to the total content of the urethane group (X) in the resin A and the curable functional group (Y) in the resin B ((number of X/(number of X+number of Y))×100) is from 1-60%.

Description

  The present invention relates to a pseudo-crosslinking curable resin composition, and a copolymer and a molded body thereof. More specifically, the present invention relates to a pseudo-crosslinking curable resin composition that can be used for a transparent conductive film that can be used for a transparent touch panel and an inner touch panel, and a copolymer and a molded body thereof.

  Conventionally, a transparent conductive film made of glass or a thermoplastic resin is generally used as a touch panel substrate. Although the touch panel substrate using the glass is excellent in transparency and environmental reliability, it has a problem that it is difficult to process because it lacks flexibility and is difficult to process, and has a problem of heavy mass. On the other hand, as the thermoplastic resin, polyethylene terephthalate, polycarbonate, alicyclic hydrocarbon polymer and the like are generally used, but a film made of such a thermoplastic resin has low heat resistance and large birefringence, A transparent conductive film made of these films and a touch panel using the transparent conductive film also have problems in heat resistance, birefringence, and the like.

  On the other hand, as a resin that can obtain a molded product having high heat resistance, polyimide, polyethersulfone, polyetherketone, polyarylate, liquid crystal polymer, and the like are generally known, but molded products made of these resins are heat resistant, Although excellent in chemical resistance and electrical insulation, since it is colored, it has been difficult to use it as an optical material requiring transparency such as the transparent conductive film.

  As a film that can be used as an optical material, for example, Patent Document 1 discloses a photosensitive transfer material containing a pseudo-crosslinked resin in order to improve heat resistance. Patent Document 2 discloses a pseudo-crosslinked resin composition in which two or more polymers are mixed to improve heat resistance and flexibility. Patent Document 3 discloses a technique for improving flexibility. Discloses a photocurable resin composition using a urethanized acrylic compound having a specific structure. However, in the molded body obtained from the resin compositions described in Patent Documents 1 to 3, although heat resistance and flexibility are obtained to some extent, it is difficult to apply to a touch panel because the elastic modulus is not sufficient. Had the problem.

JP 2003-248304 A JP 2002-38036 A JP 2006-28499 A JP-A-6-166737

  The curable acrylate is a resin capable of obtaining a highly heat-resistant molded body having excellent light transmittance. Further, by increasing the functional group content, a molded body having a high elastic modulus can be obtained. However, if the amount of the functional group is increased, the elongation at break of the obtained molded product is reduced and it is easily broken, so that the toughness and workability are inferior, and the obtained molded product cannot be made into a roll film. Had. Patent Document 4 describes a molded product obtained by curing a specific urethane / unsaturated organooligomer and acrylate. However, the elastic modulus and elongation at break are still insufficient in the molded product. It was.

  The present invention has been made in view of the above-described problems of the prior art, and is a pseudo-crosslinking type curable resin having a sufficient elastic modulus and capable of obtaining a molded article having excellent elongation at break. It aims at providing a composition, its copolymer, and a molded object.

  As a result of intensive studies to achieve the above object, the present inventors have determined that the resin A having a urethane group and the resin B having a curable functional group are the total content of the urethane group and the curable functional group. By radical copolymerizing the pseudo-crosslinked curable resin composition contained so that the content of the urethane group at a specific ratio is sufficient, it has a sufficient elastic modulus and has an excellent elongation at break. It has been found that a copolymer and a molded product can be obtained, and the present invention has been completed.

  That is, the pseudo-crosslinking curable resin composition of the present invention has the following general formula (1):

[In Formula (1), R ¹ may be the same or different and each represents a hydrogen atom or a methyl group; R ² may be the same or different and each represents an alkylene group having 1 to 12 carbon atoms; It consists of a bivalent aromatic hydrocarbon group having 6 to 12 carbon atoms, a (poly) oxyalkylene group having 2 to 12 carbon atoms, and a divalent group having 7 to 12 carbon atoms including an aromatic ring and an oxyalkylene group. Represents any one group selected from the group, and R ³ may be the same or different and each represents an alkylene group, a hydrocarbon group having a divalent alicyclic skeleton, a divalent aromatic hydrocarbon group, 1 represents any one group selected from the group consisting of an ether group, an ester group, a carbonate group, and a divalent group in which two or more of these groups are bonded, and R ⁴ is the same or different. Each of the following general formulas (2 ):

[In Formula (2), R ⁵ represents a divalent aromatic hydrocarbon group or a C 2-12 divalent aliphatic hydrocarbon group which may have a substituent. ]
A represents an integer of 0 or 1, n represents an integer of 0 to 200, n is 1 or more when a is 0, and a is 1 when n is 0. is there. ]
Resin A represented by:
A resin B having at least one curable functional group (Y) selected from the group consisting of a vinyl group, an allyl group, and a (meth) acryloyl group, and having no urethane group;
The mass ratio of the resin A to the resin B (resin A: resin B) is 10:90 to 90:10,
Ratio of content of urethane group (X) to total content of urethane group (X) in resin A and curable functional group (Y) in resin B ((number of X / (number of X The number of + Y)) × 100) is 1 to 60%.

  The number average molecular weight of the resin A is preferably 500 to 50,000, and 10 to 100% by mass of the resin B is preferably an alicyclic unsaturated compound. Moreover, it is preferable that the pseudo-crosslinking curable resin composition of the present invention further contains a radical polymerization initiator.

The copolymer of the present invention and the molded body of the present invention are obtained by radical copolymerization of the pseudo-crosslinking curable resin composition. The molded article of the present invention includes the following (i) to (iii):
(I) The elongation at break is 10% or more,
(Ii) The elastic modulus is 1000 MPa or more,
(Iii) It is preferable that the transmittance of visible light having a wavelength of 400 to 800 nm satisfies the condition of 85% or more.

  In addition, although the reason that the said objective is achieved by the pseudo-crosslinking type curable resin composition of the present invention, the copolymer and the molded body is not necessarily clear, the present inventors speculate as follows. That is, in the present invention, the following formula (3):

[In formula (3), ^{R 5} has the same meaning as ^{R 5} in formula (2). ]
As shown by the formula, the resin A is pseudo-crosslinked within the molecule or between the molecules by the hydrogen bond between the urethane groups (—NH—COO—) derived from the resin A and the intermolecular interaction due to the intermolecular force. The This pseudo-crosslinked structure is a reversible structure in which the interaction becomes strong at room temperature (about 25 ° C.) and the interaction becomes weak at high temperature (about 100 ° C. or higher). In a state where there is no impact at room temperature or impact, the crosslink density is high and a sufficient elastic modulus is exhibited. On the other hand, when external stimulation such as thermal energy is applied, the crosslink is released and another urethane group is renewed. The present inventors infer that it is difficult to break because the impact from the outside is reduced by forming a simple cross-linked structure.

  Further, in the copolymer and molded product of the present invention obtained using the pseudo-crosslinking curable resin composition of the present invention, it has a sufficient elastic modulus as described above, and has an excellent elongation at break. Therefore, it is excellent in workability, and can be stably formed into a transparent conductive film having good winding properties even when rolled, and in the pseudo-crosslinking curable resin composition of the present invention, Since a curable acrylate is used, a highly heat-resistant molded article having excellent light transmittance and low birefringence can be obtained. Therefore, the present inventors believe that the pseudo-crosslinking curable resin composition of the present invention, and the copolymer and molded body thereof can be suitably used for a transparent conductive film that can be used for a transparent touch panel and an inner touch panel. Et al.

  According to the present invention, a pseudo-crosslinking curable resin composition capable of obtaining a molded article having a sufficient elastic modulus and excellent elongation at break, and a copolymer and a molded article thereof are obtained. It becomes possible to provide.

  Hereinafter, the present invention will be described in detail with reference to preferred embodiments thereof.

  First, the pseudo-crosslinking curable resin composition of the present invention will be described. The pseudo-crosslinking curable resin composition of the present invention is characterized by containing a resin A and a resin B.

  Resin A according to the present invention has the following general formula (1)

It is represented by In the formula (1), R ¹ may be the same or different and each represents a hydrogen atom or a methyl group, and R ² may be the same or different and each represents an alkylene group having 1 to 12 carbon atoms, It consists of a bivalent aromatic hydrocarbon group having 6 to 12 carbon atoms, a (poly) oxyalkylene group having 2 to 12 carbon atoms, and a divalent group having 7 to 12 carbon atoms including an aromatic ring and an oxyalkylene group. Any one group selected from the group is shown. When the carbon number of R ² exceeds the upper limit, the resulting molded article has a low elastic modulus. Examples of the divalent aromatic hydrocarbon group having 6 to 12 carbon atoms include a phenylene group represented by the following formula (i), a biphenylene group represented by the following formula (ii), and a naphthalene represented by the following formula (iii). Examples of the (poly) oxyalkylene group having 2 to 12 carbon atoms include (poly) ethylene glycol group, (poly) propylene glycol group, (poly) butylene glycol group, and (poly) pentylene glycol group. And (poly) hexylene glycol group, and the divalent group having 7 to 12 carbon atoms including the aromatic ring and the oxyalkylene group includes a divalent phenol represented by the following formula (iv) and a carbon number. What condensed 2-6 glycol etc. are mentioned. Among these, R ² is preferably an alkylene group having 2 to 3 carbon atoms (ethylene group, propylene group) or the like from the viewpoint that a molded article having a sufficient elastic modulus and low water absorption can be obtained.

The R ^{3 s} may be the same or different and are each an alkylene group, a hydrocarbon group having a divalent alicyclic skeleton, a divalent aromatic hydrocarbon group, an ether group, an ester group, a carbonate group, and these Any one group selected from the group consisting of a divalent group to which two or more of the groups are bonded is shown. Examples of such R ³ include the following formula:
_{^{-R 6 -, - R 6 -}} (OR 6) b -, - R 6 (COOR 6) b -, - R 6 - (OCO-R 6 -COO-R 6) b -, - R 6 OCOO-R ⁶ -OCOOR ^6-
[In each formula, R ⁶ may be the same or different and each is selected from the group consisting of an alkylene group, a hydrocarbon group having a divalent alicyclic skeleton, and a divalent aromatic hydrocarbon group. 1 group is shown, b may be same or different and shows the integer of 1-20, respectively. ]
And a divalent group in which an oxyalkylene group is added to these groups.

In R ⁶ , the alkylene group preferably has 2 to 12 carbon atoms, and the hydrocarbon group having a divalent alicyclic skeleton preferably has 6 to 20 carbon atoms, The divalent aromatic hydrocarbon group preferably has 6 to 20 carbon atoms. When the carbon number of R ⁶ is less than the lower limit, the elongation at break of the obtained molded product tends to decrease, and when it exceeds the upper limit, the elastic modulus of the molded product tends to be lowered. Examples of the hydrocarbon group having a divalent alicyclic skeleton in R ⁶ include a group having a cyclohexyl skeleton represented by the following formula (v), a group having a tricyclodecane skeleton represented by the following formula (vi), and the like. Examples of the divalent aromatic hydrocarbon group include a phenylene group represented by the above formula (i), a biphenylene group represented by the above formula (ii), and a naphthalene disubstituted group represented by the above formula (iii). And groups having a bisphenol A residue represented by the following formula (vii). Moreover, as said b, it is preferable that it is an integer of 1-20 from a viewpoint that the molded object which has sufficient elasticity modulus is obtained, and it is more preferable that it is an integer of 1-10.

The oxyalkylene group is preferably an oxyalkylene group composed of an alkylene group having 2 to 12 carbon atoms from the viewpoint that a molded product having a sufficient elastic modulus tends to be obtained. ) Ethylene glycol group, (poly) propylene glycol group, (poly) butylene glycol group, (poly) pentylene glycol group, (poly) hexylene glycol group, etc., and when these oxyalkylene groups are two or more The block may be a block addition or a random addition. The number of oxyalkylene groups added is preferably 1 to 20 in R ³ from the viewpoint that a molded product having a sufficient elastic modulus tends to be obtained.

Among these, as R ³ , a group having a tricyclodecane skeleton or a group having a bisphenol A residue from the viewpoint that a molded article having a sufficient elastic modulus and a low water absorption rate tends to be obtained. For example, a group represented by the following formula (viii) is preferable.

The R ⁴ may be the same or different and each is represented by the following general formula (2):

Is a pseudo-crosslinking site represented by Since the resin A according to the present invention has a portion represented by the formula (2), the resin A has at least two urethane groups. Therefore, in the molded product obtained by the resin composition of the present invention, pseudo-crosslinking A structure can be formed, a sufficient elastic modulus can be obtained, and an excellent breaking elongation can be obtained.

In the above formula (2), R ⁵ represents a divalent aliphatic hydrocarbon group of divalent aromatic which may have a substituent hydrocarbon group or 2 to 12 carbon atoms. The divalent aromatic hydrocarbon group preferably has 6 to 30 carbon atoms. When the carbon number of R ⁵ is less than the lower limit, the elongation at break of the obtained molded product tends to decrease. On the other hand, when the upper limit is exceeded, the elastic modulus of the molded product tends to decrease. Examples of the divalent aromatic hydrocarbon group which may have a substituent include 1,3-phenylene group, 1,4-phenylene group, toluene-2,4-diyl group, toluene-2,6- Diyl group, (o, m or p) -xylenediyl group, triphenylenethiophosphate group reacted with tris (isocyanatephenyl) thiophosphate, naphthalene-1,5-diyl group, biphenylene group represented by the above formula (ii) And a diphenylmethane diisocyanate residue represented by the following formula (ix), a bis (1,4-phenylene) methylene group, and the like. The divalent aliphatic hydrocarbon group having 2 to 12 carbon atoms is represented by the following formula (x) in which a pentamethylene group, a hexamethylene group, a diphenylmethylene group, a trimethylhexamethylene group, and isophorone diisocyanate are reacted. 1-methylene-1,3,3-trimethylcyclohexane-5-yl group, cyclohexane-1,3-dimethylene group, cyclohexane-1,4-dimethylene group, methylenebis (cyclohexynyl) group, represented by the following formula (xi) And hydrogenated diphenylmethane diisocyanate residues. Among these, from the viewpoint that a molded product having a sufficient elastic modulus tends to be obtained, the R ⁵ is a 1-methylene-1,3,3-trimethylcyclohexane-5-yl group reacted with isophorone diisocyanate. , Toluene-2,4-diyl group, and toluene-2,6-diyl group are preferable.

  In the formula (1), a represents an integer of 0 or 1, n represents an integer of 0 to 200, n is 1 or more when a is 0, and a is 1 when n is 0. When the value of a exceeds the upper limit, the elastic modulus of the molded body obtained is low, and even when the value of n exceeds the upper limit, the elastic modulus of the molded body is low. As said n, it is preferable that it is 0-50 from a viewpoint that it exists in the tendency for the molded object which has the more outstanding elasticity modulus to be obtained.

  The resin A can be produced by appropriately using a known method. For example, the resin A is obtained by reacting an acrylate compound with a urethane oligomer obtained by a reaction between a diol compound and a diisocyanate compound.

  Examples of the diol compound include ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, a diol having a cyclohexyl skeleton represented by the following formula (xiii), and a tricyclodecane skeleton represented by the following formula (xiii). Diols, bisphenol A, and the like, and those obtained by adding a glycol compound having 2 to 12 carbon atoms such as ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, and the like. As such a diol compound, one of these may be used alone, or two or more may be mixed and used. Among these, a diol having a tricyclodecane skeleton, bisphenol A, and a glycol system having 2 to 12 carbon atoms, from the viewpoint of obtaining a molded article having a sufficient elastic modulus and a low water absorption rate. It is preferable to use a compound added with a compound.

  Examples of the diisocyanate compound include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, isophorone diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, (o, m or p) -xylene diisocyanate, and methylene bis (cyclohexyl isocyanate). , Trimethylhexamethylene diisocyanate, 1,3- or 1,4- (isocyanatomethyl) cyclohexane, 1,5-naphthalene diisocyanate, etc., and even if one of these is used alone, two or more may be mixed. May be used. Among these, it is preferable to use 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, and isophorone diisocyanate as the diisocyanate compound from the viewpoint of obtaining a molded product having a sufficient elastic modulus.

  Examples of the acrylate compound include monofunctional hydroxy group-containing (meth) acrylate compounds such as hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate, and one of these may be used alone. Two or more kinds may be mixed and used.

  As the reaction, for example, first, the number of isocyanate groups derived from the diisocyanate compound is excessive with respect to the number of hydroxyl groups derived from the diol compound (preferably the number of isocyanate groups relative to the number of hydroxyl groups is And the mixture is reacted at 50 to 90 ° C. for 2 to 8 hours, and then the reaction product and the acrylate compound are mixed at a molar ratio of 1: 2 to 1: 2.4. And a method of reacting the mixture at 50 to 90 ° C. for 2 to 8 hours.

  The resin A preferably has a molecular weight of 200 to 100,000 in terms of number average molecular weight, and more preferably 500 to 50,000. If the number average molecular weight is less than the lower limit, the processability of the resulting molded product tends to deteriorate, whereas if the upper limit is exceeded, the resulting molded product becomes too flexible and can be applied to a touch panel. It tends to be difficult. In addition, such a number average molecular weight is gel permeation chromatography (GPC) (device name: HLC-8320GPC (manufactured by Tosoh Corporation), solvent: THF, column: ultra-high-speed semi-micro SEC column SuperH series, temperature: 40 ° C., speed : 0.6 ml / min), and converted to standard polystyrene.

  As such resin A, 1 type may be used independently or 2 or more types may be used in combination. In addition, examples of the resin A include bifunctional urethane-modified (meth) acrylates, and resin products containing the same are commercially available, and such resin products may be used in the resin composition of the present invention. Good. Examples of the commercially available resin products include urethane acrylate oligomer UF-8001 (number average molecular weight: 2600, manufactured by Kyoeisha Chemical Co., Ltd.) and UF-503 (number average molecular weight: 3800, manufactured by Kyoeisha Chemical Co., Ltd.), urethane. Acrylate UA-122P (number average molecular weight: 1100, manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD UXT-6000 (number average molecular weight: 6000, manufactured by Nippon Kayaku Co., Ltd.), and the like.

  Resin B according to the present invention is a compound having at least one curable functional group (Y) selected from the group consisting of a vinyl group, an allyl group, and a (meth) acryloyl group, and having no urethane group. is there. Since the resin B has such a curable functional group (Y), it is radically copolymerized in the molecule of the resin B or between the molecules, or between the resin B molecule and the resin A molecule. And a high heat-resistant molded article with low birefringence can be obtained.

  As the resin B, a reactive oligomer that is a polymer having about 2 to 20 repeating structural units, a reactive monomer that has a low molecular weight and a low viscosity, a copolymer of two or more of these, and These copolymers are roughly divided into copolymers of these resins B and other resins, and the reactive monomer further includes a monofunctional unsaturated compound having one curable functional group and two or more curable functional groups. The polyfunctional unsaturated compound is roughly classified.

  Examples of the reactive oligomer include unsaturated polyester, polyester-modified (meth) acrylate, unsaturated polyester, polyester-modified (meth) acrylate, polyether (meth) acrylate, polyvinyl (meth) acrylate, silicone (meth) acrylate, polybutadiene, Examples include polystyrylethyl methacrylate, (meth) acryloyl group-containing polymethyl methacrylate, and the like.

  Among the reactive monomers, examples of the monofunctional unsaturated compound include butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, and n-decyl (meth). Acrylate, n-lauryl (meth) acrylate, n-stearyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, trifluoroethyl methacrylate, amide-modified (meth) acrylate, aminoalkyl ( (Meth) acrylate (for example, N, N′-dimethylaminoethyl (meth) acrylate), styrene, vinyl acetate, N-vinylpyrrolidone, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, epoxy Meth) acrylate, epoxidized oil (meth) acrylate.

Among the reactive monomers, the polyfunctional unsaturated compounds include bisphenol A-modified (meth) acrylate, bisphenol F-modified (meth) acrylate, tripropylene glycol di (meth) acrylate, 1,6-hexanediol di (meth). ) Acrylate, bisphenol A diglycidyl ether di (meth) acrylate, tetraethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate hydroxypivalate, pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ] pentadecane dimethylol di (meth) acrylate, dicyclopentanyl di (meth) acrylate (or tricyclo [5.2.1.0 ^2,6 ] decane dimethylol di (meth) acrylate), tri Examples include methylolpropane tri (meth) acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, and dipentaerythritol hexaacrylate.

  As the copolymer of two or more kinds of the resin B and the copolymer of the resin B and another resin, (meth) acrylic acid- (meth) acrylate copolymer, (meth) acrylic acid-substituted Styrene copolymer, (meth) acrylate- (meth) acrylamide copolymer, (meth) acrylate-aminoalkyl (meth) acrylate copolymer, styrene- (meth) acrylic acid copolymer, styrene-substituted styrene copolymer Examples thereof include a vinyl chloride-vinyl acetate copolymer and an α-olefin- (meth) acrylic acid copolymer. Moreover, these copolymers may be block copolymers or random copolymers.

As the resin B according to the present invention, any one of the resins B may be used alone or in combination of two or more. However, as the resin B according to the present invention, low water absorption and From the viewpoint that a low-hygroscopic molded product tends to be obtained, 10 to 100% by mass of the resin B is preferably an alicyclic unsaturated compound. As the alicyclic unsaturated compound, among the resin B, pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ] pentadecane dimethylol di (meth) acrylate, dicyclopentanyl di (meth) acrylate (or tricyclo [5.2.1.0 ^2,6 ] decane dimethylol di (meth) acrylate) and the like. Can be mentioned.

  Moreover, as resin B which concerns on this invention, it is preferable that 10-100 mass% of the said resin B is the said polyfunctional unsaturated compound from a viewpoint that it exists in the tendency which can form a favorable three-dimensional crosslinked body. . Furthermore, as the resin B, average curing per molecule in the resin B from the viewpoint that a good three-dimensional crosslinked product tends to be formed and a molded product excellent in heat resistance and strength tends to be obtained. The number of functional functional groups is preferably 1.1 or more, more preferably 1.5 or more, and even more preferably 1.6 to 6. Such average number of curable functional groups can be adjusted by appropriately mixing the monofunctional unsaturated compound and the polyfunctional unsaturated compound having 2 to 6 curable functional groups.

  The resin B preferably has a molecular weight of 100 to 2000 in terms of number average molecular weight, and more preferably 200 to 1500. When the number average molecular weight is less than the lower limit, the moldability tends to deteriorate, and when the number average molecular weight exceeds the upper limit, the elastic modulus of the obtained molded article tends to decrease. In addition, such a number average molecular weight is a value obtained by measuring with the above-mentioned GPC and converting with standard polystyrene.

In the present invention, as such a resin B, dicyclopentanyl di (meth) acrylate (or tricyclo [5.2. ^1.02,6 ] decane dimethylol di (meth) acrylate), phenoxyethyl acrylate, and polyester-modified diacrylate are preferably used, and dicyclopentanyl di (meth) acrylate (or tricyclo [5.2.1]. .0 ^2,6] it is more preferable to use a decane dimethylol di (meth) acrylate). Moreover, as said resin B, the resin product containing this is marketed, for example, Kyoeisha Chemical Co., Ltd. light acrylate DCP-A, light acrylate BP-4EA, light acrylate BP-4PA, light ester BP -2EMK, epoxy ester 3002M, epoxy ester 3002A, epoxy ester 3000A, epoxy ester 80MFA; Shin-Nakamura Chemical Co., Ltd. BPE-500; Nippon Kayaku Co., Ltd. KAYARAD HX-220, etc. It can be used as a raw material for the composition.

  The mass ratio of the resin A and the resin B (resin A: resin B) in the pseudo-crosslinking curable resin composition of the present invention is 10:90 to 90:10, and 15:85 to 80:20. It is preferably 15:85 to 70:30. When the content of the resin A is less than the lower limit, the elongation at break of the molded article after curing tends to be lowered, and the workability tends to be lowered. On the other hand, if the content of the resin A exceeds the upper limit, the proportion of the pseudo-crosslinked structure increases, and the viscosity of the composition may increase, so that it tends to be difficult to produce a molded body, There is a tendency for the water absorption of the resulting molded product to increase.

  In the pseudo-crosslinking curable resin composition of the present invention, the urethane group (X) with respect to the total content of the urethane group (X) in the resin A and the curable functional group (Y) in the resin B. The content ratio ((number of X / (number of X + number of Y)) × 100) is 1 to 60%. When the proportion of the content of the urethane group (X) is less than the lower limit, the elongation of the obtained molded product is lowered, and on the other hand, the proportion of the content of the urethane group (X) exceeds the upper limit, The water absorption rate of the molded body increases. Moreover, it is preferable that the ratio of content of the said urethane group (X) is 5 to 60% from a viewpoint that it exists in the tendency which a lower water absorption and a low hygroscopic molded object are obtained.

  In the present invention, the content of the urethane group (X) in the resin A is the number average molecular weight of the resin A and the resin as the molecular weight of the resin A and the number of urethane groups (X) per molecule of the resin A, respectively. A is a numerical value expressed using the average number of urethane groups (X) per molecule. In addition, such a number average molecular weight is obtained by measuring with the above-mentioned GPC and converting with standard polystyrene. The average number of urethane groups (X) per molecule is compared with the peak intensity of the terminal curable functional group and the urethane group by quantitative 13C-NMR spectrum (device name: JNM-ECA400 (manufactured by JEOL)). It is a value derived by Further, the content of the curable functional group (Y) in the resin B is also expressed in the same manner as the content of the urethane group (X) in the resin A, and the number of curable functional groups (Y) per molecule is This is a value determined by quantitative 13C-NMR spectrum (device name: JNM-ECA400 (manufactured by JEOL)).

  The pseudo-crosslinking curable resin composition of the present invention preferably further contains a radical polymerization initiator such as a thermal polymerization initiator or a photopolymerization initiator. By containing the radical polymerization initiator, radical copolymerization of the pseudo-crosslinking curable resin composition tends to be promoted, and physical properties of the obtained copolymer tend to be improved.

  The thermal polymerization initiator is a radical polymerization initiator that generates radicals by heat. Examples of such a thermal polymerization initiator include various organic peroxides, and examples of the organic peroxide include ketone peroxide. Examples thereof include oxides, diacylalkyl peroxides, hydroperoxides, dialkyl peroxides, peroxyketals, alkyl peresters, and carbonates. Among these, although not particularly limited, it is more preferable to use a dialkyl peroxide from the viewpoint of catalytic activity. Specific examples of the dialkyl peroxide include cyclohexanone peroxide, 1,1-bis (t-hexaperoxy) cyclohexanone, cumene hydroperoxide, dicumyl peroxide, benzoyl peroxide, diisopropyl peroxide, di- Examples include t-butyl peroxide, t-hexylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethylhexanoate, and among these, cyclohexanone peroxide, cumene hydroperoxide, dicumyl peroxide. More preferably, benzoyl peroxide and di-t-butyl peroxide are used.

  As the photopolymerization initiator, it is more preferable to use compounds such as acetophenone, benzoin, benzophenone, thioxanthone, and acylphosphine oxide. Specific examples of the compound include biacetylacetophenone, benzophenone, benzyl, benzoylisobutyl ether, benzyldimethyl ketal, (1-hydroxy-1-methylethyl) phenyl ketone, (α-hydroxyisopropyl) (p-isopropylphenyl). ) Ketone, diethylthioxanthone, ethyl anthraquinone, bis (diethylamino) benzophenone, trichloroacetophenone, diethoxyacetophenone, 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-hydroxy-cyclohexyl-phenyl ketone, 2 -Hydroxy-2-methyl-1-phenyl-propan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, benzoin methyl ether Examples include benzyldimethyl ketal, thioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, methylphenylglyoxylate, camphorquinone, anthraquinone, Michler's ketone, etc. Among these, (1-hydroxy-1-methylethyl) Use of phenyl ketone, 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-hydroxy-cyclohexyl-phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one Further preferred.

  As said radical polymerization initiator, these may be used independently or may be used in combination of 2 or more type. Moreover, when using the said thermal polymerization initiator, it is preferable to use a thermal polymerization accelerator together, and when using the said photoinitiator, it is preferable to use a photoinitiator adjuvant. When the radical polymerization initiator is contained, the content thereof is not particularly limited as long as it is an effective amount, but is generally 0.01 to 100 parts by mass of the total amount of the resin A and the resin B. 20.0 parts by mass, preferably 0.1-10.0 parts by mass, more preferably 0.1-5 parts by mass, and even more preferably 0.1-3 parts by mass. . If the content is less than the lower limit, the curing becomes insufficient, so that the strength and rigidity of the resulting molded product tend to be low. There is.

  As the pseudo-crosslinking curable resin composition of the present invention, a filler, a modifier, an organic / inorganic filler, a plasticizer, a flame retardant, a heat stabilizer, an oxidation, and the like within the range not impairing the object of the present invention. Inhibitors, light stabilizers, UV absorbers, lubricants, antistatic agents, mold release agents, foaming agents, nucleating agents, colorants, crosslinking agents, dispersion aids, anti-aging agents, leveling agents, wettability improvers, interfaces Additives such as an activator and a resin other than the resin A and the resin B can be added. Specifically, for example, as the filler, polyamide, polyamideimide, polyether, polyester, petroleum resin, xylene resin, epoxy resin, ketone resin, cellulose resin, fluorine oligomer, silicone oligomer, polysulfide oligomer, Examples of the modifier include silica, alumina, glass beads, styrene polymer particles, divinylbenzene polymer particles, methacrylate polymer particles, ethylene polymer particles, and propylene polymer particles. . As said additive, 1 type may be used independently or may be used in combination of 2 or more type, and the content in the case of containing the said additive is 100 mass parts of total amounts of the said resin A and the said resin B The amount is preferably 20 parts by mass or less.

  The pseudo-crosslinking curable resin composition of the present invention preferably further contains a silane coupling agent from the viewpoint of improving adhesiveness. Examples of the silane coupling agent include epoxy silanes such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane; N -Amino-silanes such as β- (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane; mercaptosilanes such as γ-mercaptosilane; Examples thereof include methyltrimethoxysilane and methyltriethoxysilane. When the silane coupling agent is contained, the content thereof is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the total amount of the resin A and the resin B.

  Subsequently, the copolymer of this invention and the molded object of this invention are demonstrated. The copolymer of the present invention is obtained by radical copolymerization of the pseudo-crosslinking curable resin composition, and the molded body of the present invention is obtained by converting the pseudo-crosslinking curable resin composition into a predetermined shape. It is a molded article of a copolymer obtained by molding into a radical copolymer. The copolymer of the present invention is a copolymer having the pseudo-crosslinked structure and a two-dimensional crosslinked structure or a three-dimensional crosslinked structure formed by curing by the radical copolymerization. As a method for obtaining a copolymer or a molded product by radical copolymerization, a known method can be adopted as appropriate, for example, a method of heating the pseudo-crosslinking curable resin composition; A method of irradiating (photoirradiating) an energy beam such as an electron beam, an ultraviolet ray and a visible ray to the resin composition can be used.

  As the heating conditions, by appropriately selecting the thermal polymerization initiator and the thermal polymerization accelerator, the reaction temperature is room temperature (about 25 ° C.) to about 200 ° C., and the reaction time is about 0.5 to 10 hours. You can choose from a wide range. The molded article of the present invention is a molded article having a desired shape by injecting the pseudo-crosslinking curable resin composition into a mold, curing it by radical copolymerization, and then removing the mold from the mold. A sheet-like molded article is manufactured by applying the pseudo-crosslinking curable resin composition on a moving steel belt using a doctor blade or a roll-shaped coater and curing it by radical copolymerization. It can obtain by the method of doing.

  Examples of the light irradiation method include a method of irradiating the pseudo-crosslinked curable resin composition with ultraviolet rays having a wavelength of 10 to 400 nm or visible rays having a wavelength of 400 to 700 nm for about 1 to 1200 seconds. The wavelength is not particularly limited, but is preferably near ultraviolet light having a wavelength of 200 to 400 nm. Examples of the lamp used as the ultraviolet ray generation source include a low pressure mercury lamp (output: 0.4 to 4 W / cm), a high pressure mercury lamp (40 to 160 W / cm), and an ultrahigh pressure mercury lamp (173 to 435 W / cm). ), Metal halide lamps (80 to 160 W / cm), pulse xenon lamps (80 to 120 W / cm), electrodeless discharge lamps (80 to 120 W / cm), and the like. Can be appropriately selected according to the type of the agent and the sharpening agent. Further, as the molded article of the present invention, the pseudo-crosslinked curable resin composition is injected into a mold composed of a transparent material such as quartz glass, cured by radical copolymerization, and then demolded from the mold. Thus, it can be obtained by a method for producing a molded body having a desired shape, a method for curing on a steel belt, or the like.

The molded article of the present invention is obtained by radical copolymerization of the pseudo-crosslinking curable resin composition, and has the pseudo-crosslinking structure and a crosslinked structure formed by curing by the radical copolymerization. According to the following (i) to (iii):
(I) The elongation at break is 10% or more,
(Ii) The elastic modulus is 1000 MPa or more,
(Iii) The transmittance of visible light having a wavelength of 400 to 800 nm can satisfy the condition of 85% or more. When the breaking elongation is less than the lower limit, it tends to be difficult to process the substrate, and when the elastic modulus is less than the lower limit, it tends to be easily deformed when used for a touch panel. The visible light transmittance is preferably 85% or more, more preferably 85% or more, and further preferably 90% or more. When the visible light transmittance is less than the lower limit, a clear image tends not to be obtained when used for a display member such as a touch panel.

  In addition, since the molded article of the present invention has high heat resistance, the substrate can be processed at high temperature in thin film deposition and the like, and since it is highly transparent and excellent in workability, for example, a transparent touch panel or inner In addition to being used for transparent conductive films that can be used for touch panels, it can also be used for optical applications such as flat panel display substrates, lenses, optical disks and optical fibers; Furthermore, since the molded article of the present invention is a transparent member excellent in light weight and impact strength, it can be used as a glass substitute material.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example.

Example 1
UA-122P containing urethane resin A (average number of urethane groups: 4, number average molecular weight: 1100) (resin A content: 80% by mass, phenoxyethyl acrylate (curable functional group: acryloyl group, average curable functional group number) 1, number average molecular weight: 236.1) content: 20% by mass, Shin-Nakamura Chemical Co., Ltd.) 20 parts by mass, polyester-modified diacrylate (curable functional group: acryloyl group, average curable functional group number) : 2, Number average molecular weight: 540.29, KAYARAD HX-220, Nippon Kayaku Co., Ltd. 35 parts by mass, dicyclopentanyl diacrylate (curable functional group: acryloyl group, average curable functional group number: 2 , Number average molecular weight: 304.38, light acrylate DCP-A, manufactured by Kyoeisha Chemical Co., Ltd.) 45 parts by mass, and 1-hydro as a photopolymerization initiator 1.0 parts by mass of xycyclohexyl phenyl ketone was mixed to obtain a transparent pseudo-crosslinking curable resin composition A. The content of urethane groups in the obtained pseudo-crosslinking curable resin composition A (ratio to the total content of urethane groups and curable functional groups in the resin A) is 12%.

Next, a pseudo-crosslinked curable resin composition A (thickness: 0.2 mm) was sandwiched between two glass plates (thickness 5 mm), and this was irradiated with light for 30 seconds using a mercury lamp (integrated exposure). Amount: 6400 mJ / cm ² ) was cured to obtain a sheet-like molded product A having a size of 200 mm × 200 mm × thickness 0.2 mm.

(Example 2)
60 parts by mass of UA-122P, instead of polyester-modified diacrylate, bisphenol A-modified dimethacrylate (curable functional group: methacryloyl group, average number of curable functional groups: 2, number average molecular weight: 804.96, BPE500, Shin Nakamura Transparent pseudo-crosslinked curable resin composition B and molded product B in the same manner as in Example 1 except that 10 parts by mass of Chemical Industry Co., Ltd. and 30 parts by mass of dicyclopentanyl diacrylate were used. Got. The urethane group content in the obtained pseudo-crosslinking curable resin composition B is 39%.

(Example 3)
Transparent pseudo-crosslinked curable resin composition as in Example 1 except that UA-122P is 80 parts by mass, polyester-modified diacrylate is 5 parts by mass, and dicyclopentanyl diacrylate is 15 parts by mass. C and molded body C were obtained. The urethane group content in the obtained pseudo-crosslinking curable resin composition C is 56%.

(Comparative Example 1)
Transparent curable resin composition D and molded body D were obtained in the same manner as in Example 1 except that UA-122P and polyester-modified diacrylate were not used and dicyclopentanyl diacrylate was changed to 100 parts by mass. . The urethane group content in the obtained curable resin composition D is 0%.

  About molded object AD obtained by Examples 1-3 and the comparative example 1, the elasticity modulus, breaking elongation, the transmittance | permeability, yellowness, and the linear expansion coefficient were measured by the method shown below, respectively. The results are summarized in Table 1.

<Measurement of elastic modulus and elongation at break>
The obtained molded body (100 mm × 8 mm × thickness 0.2 mm) is ruptured using a strograph VES5D manufactured by Toyo Seiki Seisakusho under the conditions of a temperature of 25 ° C., a distance between chucks of 30 mm, and a pulling speed of 5 mm / min. Load (N) and the displacement (mm) of the test piece length were measured, and the load (N) when the displacement was 0.2 mm to 0.4 mm was measured in units of 0.01 mm.
The slope (N / mm) when the vertical axis is the tensile load (N) and the horizontal axis is the displacement (mm) is calculated by the least square method, and the elastic modulus is expressed by the following formula:
Elastic modulus (MPa) = Inclination (N / mm) × Initial specimen length (mm) ÷ Initial specimen cross section (
mm ² )
Calculated by
The elongation at break is given by the following formula:
Elongation at break (%) = displacement (mm) / initial specimen length (mm) × 100
Calculated by

<Measurement of transmittance>
About the obtained molded object (thickness 0.2mm), the transmittance | permeability in wavelength 550nm was measured using JASCO Corporation ultraviolet visible spectrophotometer V-660.
The transmittance is the following formula:
The transmittance (%) was calculated from the transmitted light intensity / incident light intensity.

<Measurement of yellowness>
It calculated based on the JIS K7373 yellowness measuring method.

<Measurement of linear expansion coefficient>
A sample (5 mm × 5 mm × thickness 1 mm (thickness 0.2 mm × 5)) obtained by laminating five obtained molded bodies was measured based on a thermomechanical analysis method using TMA4000SA manufactured by BRUKER (increase) (Temperature rate 5 ° C./min, temperature range: 50 to 150 ° C.).
The coefficient of linear expansion is:
Linear expansion coefficient (ppm / K) = displacement amount per 1 m of test piece / temperature displacement amount.

  As is clear from the results shown in Table 1, it was confirmed that the molded articles of the present invention obtained in Examples 1 to 3 had a sufficient elastic modulus and an excellent elongation at break.

  As described above, according to the present invention, a pseudo-crosslinking curable resin composition capable of obtaining a molded article having a sufficient elastic modulus and excellent elongation at break, and a co-polymerization thereof. A polymer and a molded body can be provided.

  In addition, since the molded article of the present invention has high heat resistance, the substrate can be processed at high temperature in thin film deposition and the like, and since it is highly transparent and excellent in workability, for example, a transparent touch panel or inner In addition to being used for transparent conductive films that can be used for touch panels, it can also be used for optical applications such as flat panel display substrates, lenses, optical disks and optical fibers; Furthermore, since the molded article of the present invention is a transparent member excellent in light weight and impact strength, it can be used as a glass substitute material and is very useful.

Claims (7)

The following general formula (1):

[In Formula (1), R ¹ may be the same or different and each represents a hydrogen atom or a methyl group; R ² may be the same or different and each represents an alkylene group having 1 to 12 carbon atoms; It consists of a bivalent aromatic hydrocarbon group having 6 to 12 carbon atoms, a (poly) oxyalkylene group having 2 to 12 carbon atoms, and a divalent group having 7 to 12 carbon atoms including an aromatic ring and an oxyalkylene group. Represents any one group selected from the group, and R ³ may be the same or different and each represents an alkylene group, a hydrocarbon group having a divalent alicyclic skeleton, a divalent aromatic hydrocarbon group, 1 represents any one group selected from the group consisting of an ether group, an ester group, a carbonate group, and a divalent group in which two or more of these groups are bonded, and R ⁴ is the same or different. Each of the following general formulas (2 ):

[In Formula (2), R ⁵ represents a divalent aromatic hydrocarbon group or a C 2-12 divalent aliphatic hydrocarbon group which may have a substituent. ]
A represents an integer of 0 or 1, n represents an integer of 0 to 200, n is 1 or more when a is 0, and a is 1 when n is 0. is there. ]
Resin A represented by:
A resin B having at least one curable functional group (Y) selected from the group consisting of a vinyl group, an allyl group, and a (meth) acryloyl group, and having no urethane group;
The mass ratio of the resin A to the resin B (resin A: resin B) is 10:90 to 90:10,
Ratio of content of urethane group (X) to total content of urethane group (X) in resin A and curable functional group (Y) in resin B ((number of X / (number of X The number of + Y)) × 100) is 1 to 60%, a pseudo-crosslinking curable resin composition.   The pseudo-crosslinking curable resin composition according to claim 1, wherein the resin A has a number average molecular weight of 500 to 50,000.   The pseudo-crosslinked curable resin composition according to claim 1 or 2, wherein 10 to 100% by mass of the resin B is an alicyclic unsaturated compound.   The pseudo-crosslinking curable resin composition according to any one of claims 1 to 3, further comprising a radical polymerization initiator.   The copolymer obtained by carrying out radical copolymerization of the pseudo-crosslinking type curable resin composition as described in any one of Claims 1-4.   The molded object obtained by radical copolymerizing the pseudo-crosslinking type curable resin composition as described in any one of Claims 1-4. The following (i) to (iii):
(I) The elongation at break is 10% or more,
(Ii) The elastic modulus is 1000 MPa or more,
(Iii) The molded article according to claim 6, wherein the transmittance of visible light having a wavelength of 400 to 800 nm satisfies a condition of 85% or more.