JP2009072990A - Laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminate with a surface layer which has high coat hardness so that it can hardly be scratched and shows excellent adhesiveness with a plastic base material. <P>SOLUTION: This laminate comprises: a base material containing a heat-resistant acrylic resin as a main component; and a layer which is obtained by applyng a resin composition containing a ketone-based solvent and a (meth)acryloyl group pendant-type polymer with a double bond which is radical-polymerizable (anionic polymerization) in the side chain, and formed on the base material. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a laminate having a scratch-resistant, high hardness surface layer. More specifically, a laminate having an acrylic resin substrate surface having high heat resistance and excellent optical properties, excellent substrate adhesion, scratch resistance, and high hardness scratch resistance layer, and using the same The present invention relates to an image display device obtained.

  In recent years, image display devices such as a liquid crystal display device, a plasma display, and an organic EL display device have been greatly challenged in suppressing an increase in weight due to an increase in screen size. In particular, in the case of image display device members, it has been considered that replacement of components that have conventionally used glass with a transparent resin is effective in reducing weight and improving productivity. Among transparent resins, acrylic resins represented by polymethyl methacrylate (hereinafter referred to as “PMMA”) are excellent in optical performance, and have been conventionally used as optically isotropic materials with high light transmittance, low birefringence, and low retardation. Although attention has been paid, acrylic resins generally have poor heat resistance, and their use has been limited to applications that do not require high heat resistance. In recent years, there has been an increasing demand for heat resistance of transparent resin materials, and high heat resistance has also been demanded for acrylic resins.

  A heat-resistant acrylic resin (hereinafter referred to as “heat-resistant acrylic resin”) is a lactone ring-containing polymer obtained by subjecting a polymer having a hydroxyl group and an ester group in a molecular chain to a lactone cyclocondensation reaction. (See, for example, Patent Documents 1, 2, 3, and 4) and maleimide copolymers obtained by copolymerizing maleimides (for example, see Patent Document 5). However, heat-resistant acrylic resins are becoming more heat resistant, but their hardness is lower than that of glass and they are easily damaged. Therefore, they may not be used for members that require scratch resistance and hardness, such as the outermost layer of image display devices. It was.

JP 2000-230016 A JP 2001-151814 A JP 2002-120326 A JP 2002-254544 A JP 09-324016 A

  Under the circumstances described above, the problem to be solved by the present invention is that the surface of the acrylic resin substrate having excellent heat resistance and optical properties is excellent in adhesion to the substrate, and scratch resistance and high hardness scratch resistance. It is providing the laminated body which has a layer, and the image display apparatus obtained using it.

  The present inventor believes that a laminate in which a scratch-resistant cured layer (hereinafter referred to as a hard coat layer) is formed for the purpose of imparting scratch resistance to the surface of the heat-resistant acrylic resin substrate is one of the solutions to the above problems. And examined. However, for example, the methods using the urethane acrylate materials disclosed in Patent Documents 6 and 7 have improved the surface hardness, but have poor adhesion to the heat-resistant acrylic resin substrate, and have been found to occur.

JP-A-2005-162908 JP, 2006-282909, A The present inventors paid attention to the combination of a heat-resistant acrylic resin base material and a hard coat layer composition, and repeated earnest examination. As a result, a laminate obtained by applying and curing a curable resin composition containing a ketone solvent and a vinyl compound on a heat-resistant acrylic resin substrate having a specific structure solves the above problems all at once, and images The inventors have found that a laminate suitable for a display device member can be obtained, and completed the present invention.

That is, the present invention is a laminate in which a layer obtained by applying a resin composition containing a ketone solvent and a vinyl compound is formed on the surface of a base material containing a heat-resistant acrylic resin as a main component.
Furthermore, it is a laminated body using the said resin composition whose content rate of a ketone solvent is 50 mass% or more as a solvent.
Furthermore, the following formula (1):

[Wherein R ¹ is an alkylene group having 2 to 8 carbon atoms, R ² is a hydrogen atom or a methyl group, and m is a positive integer]
It is a laminated body of the said description containing the vinyl polymer which has a repeating unit shown by these.
Furthermore, it is an image display device obtained by using the laminate described above.

  ADVANTAGE OF THE INVENTION According to this invention, the laminated body which has the hardened layer which maintains the transparency and optical characteristic of a heat-resistant acrylic resin base material, has high surface hardness, and is hard to be damaged is obtained. Further, the heat-resistant acrylic resin base material is less likely to warp or curl when the laminate is produced, and has excellent adhesiveness with the heat-resistant acrylic resin base material, and has good moldability. The laminate of the present invention is suitable for use in an image display device.

≪Heat-resistant acrylic substrate≫
This invention is a laminated body with a heat-resistant acrylic resin base material. This will be described in detail below.
(1. Heat-resistant acrylic resin)
The heat-resistant acrylic resin used in the present invention is a resin obtained by polymerizing acrylic acid, methacrylic acid and derivatives thereof as a main component and derivatives thereof, and is not particularly limited as long as the effects of the present invention are not impaired. A methacrylic acid thermoplastic resin can be used. For example, the general formula (3)

(In the formula, R 1 and R 2 each independently represent a hydrogen atom or an organic residue having 1 to 20 carbon atoms. Specifically, the organic residue is a linear or branched chain having 1 to 20 carbon atoms. Indicates a chain or cyclic alkyl group.)
Preferable specific examples of the compound (monomer) having a structure represented by the formula, acrylic acid, methacrylic acid and derivatives thereof include methyl (meth) acrylate, ethyl (meth) acrylate, n- (meth) acrylate. Propyl, n-butyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, 2-chloroethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth ) 3-hydroxypropyl acrylate, 2,3,4,5,6-pentahydroxyexyl (meth) acrylate and 2,3,4,5-tetrahydroxypentyl (meth) acrylate. Among these, only 1 type may be used and 2 or more types may be used together. Of these, methyl (meth) acrylate is most preferred because of its excellent thermal stability.

  In addition, from the viewpoint of heat resistance, methacrylic thermoplastic resins may be copolymerized with N-substituted maleimides such as phenylmaleimide, cyclohexylmaleimide and methylmaleimide, or in the molecular chain (in the main skeleton in the polymer). Alternatively, a lactone ring structure, a glutaric anhydride structure, a glutarimide structure, or the like may be introduced into the main chain).

  Especially, the structure which does not contain a nitrogen atom is preferable at the point of the difficulty of coloring (yellowing) of a plastic base material. Moreover, the thing which has a lactone ring structure in a principal chain from the point which is easy to express a positive birefringence (positive phase difference) is preferable. Regarding the lactone ring structure in the main chain, a 4- to 8-membered ring may be used, but a 5- to 6-membered ring is more preferable, and a 6-membered ring is particularly preferable in terms of the stability of the structure. As described above, examples of the case where the lactone ring structure in the main chain is a 6-membered ring include a general formula (4) described later and a structure represented in JP-A No. 2004-168882. When synthesizing a polymer before introducing a lactone ring structure into the polymer, it is possible to obtain a polymer having a high polymerization yield, a polymer having a high content of lactone ring structure with a high polymerization yield, methyl methacrylate, etc. It is preferable that it is a structure represented by General formula (4) at a point with good copolymerizability with (meth) acrylic acid ester.

  Moreover, these acrylic resins may have a unit obtained by copolymerizing other monomer components that can be copolymerized within a range not impairing heat resistance. Specific examples of other monomer components that can be copolymerized include aromatic vinyl monomers such as styrene and α-methylstyrene, nitrile monomers such as acrylonitrile, vinyl esters such as vinyl acetate, and the like. Is given.

  The weight average molecular weight of the acrylic resin is preferably in the range of 1,000 to 2,000,000, more preferably in the range of 5,000 to 1,000,000, and still more preferably 10,000. It is in the range of not less than 500,000, particularly preferably not less than 50,000 and not more than 500,000.

  It does not specifically limit as a method to manufacture the said acrylic resin, What is necessary is just to superpose | polymerize the monomer composition containing (meth) acrylic acid ester using a conventionally well-known method.

  The polymerization temperature and the polymerization time vary depending on the type of monomer (monomer composition) used, the ratio of use, and the like. Preferably, the polymerization temperature is in the range of 0 ° C. to 150 ° C., and the polymerization time is 0.00. It is in the range of 5 hours to 20 hours, more preferably, the polymerization temperature is in the range of 80 ° C. to 140 ° C., and the polymerization time is in the range of 1 hour to 10 hours.

  In the case of a polymerization form using a solvent, the polymerization solvent is not particularly limited. For example, aromatic hydrocarbon solvents such as toluene, xylene, and ethylbenzene; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; ether solvents such as tetrahydrofuran Etc., and only one of these may be used, or two or more may be used in combination. When producing the lactone ring-containing polymer described later, if the boiling point of the solvent used is too high, the residual volatile content of the lactone ring-containing polymer finally obtained increases, so the boiling point is 50 ° C. or higher and 200 ° C. Those within the following ranges are preferred.

  During the polymerization reaction, a polymerization initiator may be added as necessary. Although it does not specifically limit as a polymerization initiator, For example, cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butylperoxyisopropyl carbonate, t-amyl Organic peroxides such as peroxy-2-ethylhexanoate; 2,2′-azobis (isobutyronitrile), 1,1′-azobis (cyclohexanecarbonitrile), 2,2′-azobis (2, Azo compounds such as 4-dimethylvaleronitrile), and the like. These may be used alone or in combination of two or more. The amount of the polymerization initiator used is not particularly limited as long as it is appropriately set according to the combination of the monomers used and the reaction conditions.

  When performing the polymerization, it is preferable to control the concentration of the produced polymer in the polymerization reaction mixture to be 50% by weight or less in order to suppress gelation of the reaction solution. Specifically, when the concentration of the produced polymer in the polymerization reaction mixture exceeds 50% by weight, it is preferable that the polymerization solvent is appropriately added to the polymerization reaction mixture and controlled to be 50% by weight or less. . The concentration of the produced polymer in the polymerization reaction mixture is more preferably 45% by weight or less, still more preferably 40% by weight or less. Note that if the concentration of the polymer in the polymerization reaction mixture is too low, the productivity is lowered. Therefore, the concentration of the polymer in the polymerization reaction mixture is preferably 10% by weight or more, and more preferably 20% by weight or more. It is more preferable.

  The form in which the polymerization solvent is appropriately added to the polymerization reaction mixture is not particularly limited, and the polymerization solvent may be added continuously or intermittently. By controlling the concentration of the produced polymer in the polymerization reaction mixture in this way, the gelation of the reaction solution can be more sufficiently suppressed, and in particular, to increase the lactone ring content and improve the heat resistance. Even when the ratio of hydroxyl groups and ester groups in the molecular chain is increased, gelation can be sufficiently suppressed.

  The polymerization solvent to be added may be the same type of solvent used during the initial charging of the polymerization reaction or may be a different type of solvent, but is the same as the solvent used during the initial charging of the polymerization reaction. It is preferable to use different types of solvents. Further, the polymerization solvent to be added may be only one type of solvent or a mixed solvent of two or more types.

  In the polymerization reaction mixture obtained when the polymerization reaction is completed, a solvent is usually contained in addition to the obtained polymer. In the case where the polymer is a lactone ring-containing polymer described in detail below, it is not necessary to completely remove the solvent and take out the polymer in a solid state. It is preferable to perform a polycondensation step. If necessary, after taking out in a solid state, a solvent suitable for the subsequent lactone cyclization condensation step may be added again.

The hue of the acrylic resin obtained by the polymerization reaction is not particularly limited, but it is preferable that it is transparent and has a lower yellowing degree because it does not impair the original characteristics of the acrylic resin. For example, the acrylic resin has a haze value of 3 or less, more preferably 2 or less, and most preferably 1 or less when formed into a 3 mm thick molded body. The molded article has a YI (yellow index) value of 10 or less, preferably 5 or less.
(2. Lactone ring-containing polymer)
As the acrylic resin, transparency, heat resistance and optical isotropy are all high, and the properties according to various optical applications can be sufficiently exhibited. It is preferable to include a so-called lactone ring-containing polymer into which a lactone ring structure has been introduced by a cyclization reaction, and it is particularly preferable to include a main component. “Main component” means that it is contained in an amount of 50% by weight or more based on the total weight of the acrylic resin. The lactone ring-containing polymer is not particularly limited, but preferably has a lactone ring structure represented by the following general formula (4).

(In the formula, R 3, R 4 and R 5 each independently represents a hydrogen atom or an organic residue having 1 to 20 carbon atoms. The organic residue may contain an oxygen atom.)
The content of the lactone ring structure represented by the general formula (4) in the lactone ring-containing polymer structure is preferably 5% by weight to 90% by weight, more preferably 10% by weight to 70% by weight, Preferably they are 10 weight% or more and 60 weight% or less, Especially preferably, they are 10 weight% or more and 50 weight% or less. When the content is less than 5% by weight, the heat resistance, solvent resistance and surface hardness may be insufficient, which is not preferable. On the other hand, when the content is more than 90% by weight, molding processability may be poor, which is not preferable.

  The lactone ring-containing polymer may have a structure other than the lactone ring structure represented by the general formula (4). The structure other than the lactone ring structure represented by the general formula (4) is not particularly limited. For example, (meth) acrylic acid ester, hydroxyl group-containing monomer, unsaturated carboxylic acid, represented by the following general formula (5) A polymer structural unit (repeating structural unit) constructed by polymerizing at least one selected from the above monomers is preferred.

(Wherein R6 represents a hydrogen atom or a methyl group, X represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, an -OAc group, a -CN group, a -CO-R7 group, or -C-O) -R8 group is represented, Ac group represents an acetyl group, R7 and R8 represent a hydrogen atom or a C1-C20 organic residue.)
In the lactone ring-containing polymer, the content ratio of the structure other than the lactone ring structure represented by the general formula (4) is that of a polymer structural unit (repeating structural unit) constructed by polymerizing (meth) acrylic acid ester. In this case, it is preferably in the range of 10% to 95% by weight, more preferably in the range of 10% to 90% by weight, still more preferably in the range of 40% to 90% by weight, particularly preferably 50%. It is in the range of not less than 90% by weight.

  In the case of a polymer structural unit (repeating structural unit) constructed by polymerizing a hydroxyl group-containing monomer, the content ratio of the structure other than the lactone ring structure represented by the general formula (4) is preferably 0 weight. % To 30% by weight, more preferably 0% to 20% by weight, even more preferably 0% to 15% by weight, particularly preferably 0% to 10% by weight. Within the following range.

  In the case of a polymer structural unit (repeating structural unit) constructed by polymerizing an unsaturated carboxylic acid, the content of the structure other than the lactone ring structure represented by the general formula (4) is preferably 0% by weight. In the range of 30 wt% or less, more preferably in the range of 0 wt% or more and 20 wt% or less, more preferably in the range of 0 wt% or more and 15 wt% or less, particularly preferably in the range of 0 wt% or more and 10 wt% or less. Is within the range.

  In addition, in the case of a polymer structural unit (repeating structural unit) constructed by polymerizing the monomer represented by the general formula (5), inclusion of a structure other than the lactone ring structure represented by the general formula (4) The ratio is preferably in the range of 0 to 30% by weight, more preferably in the range of 0 to 20% by weight, still more preferably in the range of 0 to 15% by weight, particularly preferably It is in the range of 0 wt% or more and 10 wt% or less.

  The method for producing the lactone ring-containing polymer is not particularly limited. Preferably, after obtaining a polymer having a hydroxyl group and an ester group in the molecular chain by a polymerization step, the polymer is heat-treated. Can be obtained by conducting a lactone ring condensation reaction for introducing a lactone ring structure into the polymer.

  By forming the lactone ring structure in the molecular chain of the polymer (in the main skeleton of the polymer), high heat resistance is imparted to the polymer. If the reaction rate of the cyclization condensation reaction leading to the lactone ring structure is insufficient, the heat resistance will not be improved sufficiently, or the condensation reaction will occur during the molding process due to the heat treatment during molding, and the resulting alcohol will be contained in the molded product. It is not preferable because it may exist as bubbles or silver streaks.

  The method for heat-treating the polymer to perform the lactone ring condensation reaction is not particularly limited, and a known method can be used. For example, you may heat-process the polymerization reaction mixture containing the solvent obtained by the superposition | polymerization process as it is. Moreover, you may heat-process using a ring-closing catalyst as needed in presence of a solvent. Further, the heat treatment can be performed using a heating furnace or reaction apparatus having a vacuum apparatus or a devolatilizing apparatus for removing volatile components, an extruder having a devolatilizing apparatus, or the like.

  When carrying out the cyclization condensation reaction, other acrylic resins may coexist in addition to the polymer. Further, when performing the cyclization condensation reaction, if necessary, an esterification catalyst or a transesterification catalyst such as p-toluenesulfonic acid generally used as a catalyst for the cyclization condensation reaction may be used. Organic carboxylic acids such as propionic acid, benzoic acid, acrylic acid, and methacrylic acid may be used as a catalyst. As disclosed in JP-A-61-254608 and JP-A-61-261303, basic compounds, organic carboxylates, carbonates and the like may be used.

  In carrying out the cyclization condensation reaction, it is preferable to use an organic phosphorus compound as a catalyst. By using an organophosphorus compound as a catalyst, the cyclization condensation reaction rate can be improved, and coloring of the resulting lactone ring-containing polymer can be greatly reduced. Furthermore, by using an organophosphorus compound as a catalyst, it is possible to suppress a decrease in molecular weight that can occur when a devolatilization step described later is used in combination, and to impart excellent mechanical strength.

  Examples of the organic phosphorus compound that can be used as a catalyst in the cyclocondensation reaction include alkyl (aryl) phosphonous acids such as methylphosphonous acid, ethylphosphonous acid, and phenylphosphonous acid (however, Tautomers (which may be alkyl (aryl) phosphinic acid) and diesters or monoesters thereof; dimethylphosphinic acid, diethylphosphinic acid, diphenylphosphinic acid, phenylmethylphosphinic acid, phenylethylphosphinic acid, etc. Dialkyl (aryl) phosphinic acids and esters thereof; alkyl (aryl) phosphonic acids such as methyl phosphonic acid, ethyl phosphonic acid, trifluoromethyl phosphonic acid, phenyl phosphonic acid, and their diesters or monoesters; Alkyl (aryl) phosphinic acids such as phosphoric acid, ethylphosphinic acid, phenylphosphinic acid and their esters; methyl phosphite, ethyl phosphite, phenyl phosphite, dimethyl phosphite, phosphorous acid Phosphorous acid diester or monoester or triester such as diethyl, diphenyl phosphite, trimethyl phosphite, triethyl phosphite, triphenyl phosphite; methyl phosphate, ethyl phosphate, 2-ethylhexyl phosphate, phosphorus Isodecyl phosphate, lauryl phosphate, stearyl phosphate, isostearyl phosphate, phenyl phosphate, dimethyl phosphate, diethyl phosphate, di-2-ethylhexyl phosphate, diisodecyl phosphate, dilauryl phosphate, distearyl phosphate, phosphorus Diisostearyl acid, diphenyl phosphate, trimethyl phosphate , Phosphoric diesters or monoesters or triesters such as triethyl phosphate, triisodecyl phosphate, trilauryl phosphate, tristearyl phosphate, triisostearyl phosphate, triphenyl phosphate; methylphosphine, ethylphosphine, phenylphosphine, dimethyl Phosphine, diethylphosphine, diphenylphosphine, trimethylphosphine, triethylphosphine, triphenylphosphine, etc. mono-, di- or trialkyl (aryl) phosphine; methyldichlorophosphine, ethyldichlorophosphine, phenyldichlorophosphine, dimethylchlorophosphine, diethylchlorophosphine, Alkyl (aryl) halogen phosphines such as diphenylchlorophosphine; Sphine, phenylphosphine oxide, dimethylphosphine oxide, diethylphosphine oxide, diphenylphosphine oxide, trimethylphosphine oxide, triethylphosphine oxide, triphenylphosphine oxide, mono-, di- or trialkyl (aryl) phosphines; tetramethylphosphonium chloride, chloride And halogenated tetraalkyl (aryl) phosphonium such as tetraethylphosphonium and tetraphenylphosphonium chloride. Among these, alkyl (aryl) phosphonous acid, phosphorous acid diester or monoester, phosphoric acid diester or monoester, and alkyl (aryl) phosphonic acid are preferable because of high catalytic activity and low colorability. ) Phosphorous acid, phosphorous acid diester or monoester, phosphoric acid diester or monoester are more preferred, and alkyl (aryl) phosphonous acid, phosphoric acid diester or monoester is particularly preferred. These organic phosphorus compounds may use only 1 type and may use 2 or more types together.

  The amount of the catalyst used in the cyclization condensation reaction is not particularly limited, but is preferably in the range of 0.001 to 5% by weight, more preferably 0.01 to 2.5% by weight with respect to the polymer. %, More preferably 0.01 to 1% by weight, particularly preferably 0.05 to 0.5% by weight. If the amount of the catalyst used is less than 0.001% by weight, the reaction rate of the cyclization condensation reaction may not be sufficiently improved. On the other hand, if the amount exceeds 5% by weight, coloring may occur, This is not preferable because it may be difficult to melt and form by crosslinking of the coalesced.

  The addition timing of the catalyst is not particularly limited, and it may be added at the beginning of the reaction, during the reaction, or both.

  It is preferable to carry out the cyclization condensation reaction in the presence of a solvent and to use a devolatilization step in combination with the cyclization condensation reaction. In this case, a mode in which the devolatilization step is used throughout the cyclization condensation reaction and a mode in which the devolatilization step is not used over the entire cyclization condensation reaction but only in a part of the process. In the method using the devolatilization step in combination, the alcohol produced as a by-product in the condensation cyclization reaction is forcibly devolatilized and removed, so that the equilibrium of the reaction is advantageous for the production side.

  The devolatilization step refers to a step of removing volatile components such as a solvent and residual monomers and alcohol produced as a by-product by a cyclocondensation reaction leading to a lactone ring structure, if necessary under reduced pressure heating conditions. If this removal treatment is insufficient, the residual volatile components in the produced resin increase, resulting in problems such as coloration due to alteration during molding, or molding defects such as bubbles or silver streaks.

  In the case of a form in which a devolatilization step is used throughout the cyclization condensation reaction, the apparatus to be used is not particularly limited, but a devolatilization apparatus comprising a heat exchanger and a devolatilization tank in order to perform the present invention more effectively. It is preferable to use an extruder equipped with a vent, or a device in which the devolatilizer and the extruder are arranged in series, and it is more preferable to use a devolatilizer comprising a heat exchanger and a devolatilization tank or an extruder equipped with a vent. preferable.

  In the case of using a devolatilizer comprising the heat exchanger and the devolatilization tank, the reaction treatment temperature is preferably in the range of 150 to 350 ° C, more preferably in the range of 200 to 300 ° C. If the reaction treatment temperature is lower than 150 ° C., the cyclization condensation reaction may be insufficient and the residual volatile matter may increase, and if it is higher than 350 ° C., coloring or decomposition may occur.

  In the case of using a devolatilizer comprising the heat exchanger and the devolatilization tank, the pressure during the reaction treatment is preferably within a range of 931 to 1.33 hPa (700 to 1 mmHg), and 798 to 66.5 hPa (600 to 50 mmHg). ) Is more preferable. When the pressure is higher than 931 hPa, there is a problem that volatile components including alcohol easily remain, and when the pressure is lower than 1.33 hPa, there is a problem that industrial implementation becomes difficult.

  When using the extruder with a vent, one or a plurality of vents may be used, but it is preferable to have a plurality of vents.

  In the case of using the vented extruder, the reaction treatment temperature is preferably in the range of 150 to 350 ° C, more preferably in the range of 200 to 300 ° C. If the temperature is lower than 150 ° C., the cyclization condensation reaction may be insufficient and the residual volatile content may increase. If the temperature is higher than 350 ° C., coloring or decomposition may occur.

  In the case of using the extruder with a vent, the pressure during the reaction treatment is preferably within a range of 931 to 1.33 hPa (700 to 1 mmHg), and more preferably within a range of 798 to 13.3 hPa (600 to 10 mmHg). When the pressure is higher than 931 hPa, there is a problem that volatile components including alcohol easily remain, and when the pressure is lower than 1.33 hPa, there is a problem that industrial implementation becomes difficult.

  In the case of using the devolatilization step throughout the cyclization condensation reaction, as described later, the physical properties of the lactone ring-containing polymer obtained may be deteriorated under severe heat treatment conditions. It is preferable to use a catalyst for a dealcoholization reaction and under a mild condition as much as possible using an extruder with a vent.

  In the case of using a devolatilization step throughout the cyclization condensation reaction, preferably, the polymer obtained in the polymerization step is introduced into the cyclization condensation reactor system together with a solvent. Then, it may be passed once again through the reactor system such as an extruder with a vent.

  You may perform the form used together only in a part of process, without using a devolatilization process over the whole process of cyclization condensation reaction. For example, the apparatus for producing the polymer is further heated, and if necessary, a part of the devolatilization step is used together to advance the cyclization condensation reaction to some extent in advance, and then the devolatilization step is used at the same time. In this mode, the cyclization condensation reaction is performed to complete the reaction.

  In the embodiment in which the devolatilization step is used throughout the cyclization condensation reaction described above, for example, when the polymer is heat-treated at a high temperature of about 250 ° C. or higher using a twin screw extruder, Depending on the difference, partial decomposition or the like may occur before the cyclization condensation reaction occurs, and the physical properties of the resulting lactone ring-containing polymer may be deteriorated. Therefore, if the cyclization condensation reaction is allowed to proceed to some extent before the cyclization condensation reaction using the devolatilization step at the same time, the latter reaction conditions can be relaxed and the physical properties of the resulting lactone ring-containing polymer deteriorated. Is preferable.

  A particularly preferred form is a form in which the devolatilization step is started after a while from the start of the cyclization condensation reaction, that is, the hydroxyl group and ester group present in the molecular chain of the polymer obtained in the polymerization step are cyclized in advance. A form in which a condensation reaction is performed to increase the cyclization condensation reaction rate to some extent, and then a cyclization condensation reaction using a devolatilization step in combination is performed. Specifically, for example, a cyclization condensation reaction is allowed to proceed to a certain reaction rate in the presence of a solvent in advance using a kettle-type reactor, and then a reactor equipped with a devolatilizer, for example, a heat Preferred is a mode in which the cyclization condensation reaction is completed with a devolatilizer comprising an exchanger and a devolatilization tank, an extruder with a vent, or the like. Particularly in this form, it is more preferable that a catalyst for the cyclization condensation reaction is present.

  As described above, the hydroxyl group and ester group present in the molecular chain of the polymer obtained in the polymerization step are subjected to a cyclization condensation reaction in advance to increase the cyclization condensation reaction rate to some extent. The method of carrying out the cyclization condensation reaction simultaneously used is a preferred form for obtaining a lactone ring-containing polymer. With this configuration, a lactone ring-containing polymer having a higher cyclization condensation reaction rate, a higher glass transition temperature, and excellent heat resistance can be obtained. In this case, as a measure of the cyclization condensation reaction rate, the weight loss rate between 150 and 300 ° C. in the dynamic TG measurement shown in the examples is preferably 2% or less, more preferably 1.5% or less. More preferably, it is 1% or less.

  The reactor that can be employed in the cyclization condensation reaction that is performed in advance before the cyclization condensation reaction using the devolatilization process at the same time is not particularly limited, but preferably an autoclave, a kettle reactor, a heat exchanger, and a devolatilization tank A vented extruder suitable for a cyclocondensation reaction in which a devolatilization step is simultaneously used can also be used. More preferred are autoclaves and kettle reactors. However, even when using a reactor such as an extruder with a vent, by adjusting the temperature condition, barrel condition, screw shape, screw operating condition, etc. It is possible to carry out the cyclization condensation reaction in the same state as the reaction state in the kettle reactor.

  In the case of the cyclization condensation reaction performed in advance before the cyclization condensation reaction using the devolatilization step at the same time, preferably, a mixture containing the polymer and the solvent obtained in the polymerization step is added (i) a catalyst. And (ii) a method of performing a heat reaction without a catalyst, and a method of performing the above (i) or (ii) under pressure.

  The “mixture containing a polymer and a solvent” to be introduced into the cyclization condensation reaction in the lactone cyclization condensation step may be the polymerization reaction mixture obtained in the polymerization step as it is, or once the solvent is removed. After that, it means that a solvent suitable for the cyclization condensation reaction may be added again.

  The solvent that can be re-added in the cyclization condensation reaction that is carried out in advance before the cyclization condensation reaction simultaneously used in the devolatilization step is not particularly limited, for example, aromatic hydrocarbons such as toluene, xylene, and ethylbenzene; Ketones such as methyl ethyl ketone and methyl isobutyl ketone; chloroform, DMSO, tetrahydrofuran and the like may be used, but the same type of solvent that can be used in the polymerization step is preferable.

  Examples of the catalyst added in the above method (i) include esterification catalysts such as p-toluenesulfonic acid or transesterification catalysts, basic compounds, organic carboxylates, carbonates and the like that are generally used. Is preferably the above-described organophosphorus compound.

  The addition timing of the catalyst is not particularly limited, and it may be added at the beginning of the reaction, during the reaction, or both. The amount of the catalyst to be added is not particularly limited, but is preferably in the range of 0.001 to 5% by weight, more preferably in the range of 0.01 to 2.5% by weight, still more preferably based on the weight of the polymer. It is in the range of 0.01 to 0.1% by weight, particularly preferably in the range of 0.05 to 0.5% by weight. The heating temperature and heating time in method (i) are not particularly limited, but the heating temperature is preferably room temperature or higher, more preferably 50 ° C. or higher, and the heating time is preferably in the range of 1 to 20 hours. More preferably, it is in the range of 2 to 10 hours. If the heating temperature is low or the heating time is short, the cyclization condensation reaction rate is lowered, which is not preferable. Further, if the heating time is too long, the resin may be colored or decomposed, which is not preferable.

  Examples of the method (ii) include a method of heating the polymerization reaction mixture obtained in the polymerization step as it is using a pressure-resistant kettle or the like. The heating temperature is preferably 100 ° C. or higher, more preferably 150 ° C. or higher. The heating time is preferably in the range of 1 to 20 hours, more preferably in the range of 2 to 10 hours. If the heating temperature is low or the heating time is short, the cyclization condensation reaction rate is lowered, which is not preferable. Further, if the heating time is too long, the resin may be colored or decomposed, which is not preferable.

  Both the above methods (i) and (ii) have no problem even under pressure depending on conditions. Moreover, in the case of the cyclization condensation reaction performed beforehand before the cyclization condensation reaction which used the devolatilization process simultaneously, even if a part of the solvent volatilizes naturally during the reaction, there is no problem.

  The weight loss rate between 150 and 300 ° C. in dynamic TG measurement at the end of the cyclization condensation reaction performed in advance before the cyclization condensation reaction simultaneously using the devolatilization step, that is, immediately before the start of the devolatilization step is 2% or less is preferable, More preferably, it is 1.5% or less, More preferably, it is 1% or less. When the weight reduction rate is higher than 2%, the cyclization condensation reaction rate does not rise to a sufficiently high level even if the cyclization condensation reaction is performed simultaneously with the devolatilization step, and the physical properties of the resulting lactone ring-containing polymer. May decrease. In addition, when performing said cyclization condensation reaction, in addition to a polymer, you may coexist other thermoplastic resins.

  The other thermoplastic resin is preferably a thermoplastic resin that is thermodynamically compatible with the lactone ring-containing polymer. For example, a copolymer containing a vinyl cyanide monomer unit and an aromatic vinyl monomer unit, specifically 50 wt.% Of an acrylonitrile-styrene copolymer, a polyvinyl chloride resin, or a methacrylic ester. % Or more of the polymer.

  Among them, acrylonitrile-styrene copolymer has the highest compatibility, and a transparent molded product can be obtained without impairing heat resistance. Note that the thermodynamic compatibility of the lactone ring-containing polymer and other thermoplastic resins should be confirmed by measuring the glass transition point of the thermoplastic resin composition obtained by mixing them. Can do. Specifically, only one point of the glass transition point measured by the differential scanning calorimeter is observed for the mixture of the lactone ring-containing polymer and the other thermoplastic resin, so that the thermodynamic compatibility is achieved. I can say that.

  When an acrylonitrile-styrene copolymer is used as the other thermoplastic resin, as a method for polymerizing a lactone ring-containing polymer and an acrylonitrile-styrene copolymer, an emulsion polymerization method, a suspension polymerization method, or a solution polymerization method is used. A bulk polymerization method or the like can be used, but it is preferably obtained by a solution polymerization method or a bulk polymerization method from the viewpoint of transparency and optical performance of the obtained film.

  Cyclization using a hydroxyl group and an ester group present in the molecular chain of the polymer obtained in the polymerization step in advance by a cyclization condensation reaction to increase the cyclization condensation reaction rate to a certain extent, followed by a devolatilization step at the same time. In the case of carrying out the condensation reaction, the polymer obtained by the cyclization condensation reaction carried out in advance (a polymer in which at least a part of the hydroxyl groups and ester groups present in the molecular chain have undergone cyclization condensation reaction) and the solvent are separated. The cyclization condensation reaction using the devolatilization step at the same time may be performed. In addition, if necessary, other treatment such as re-addition of the solvent after separating the polymer (polymer in which at least a part of the hydroxyl group and ester group present in the molecular chain has undergone cyclocondensation reaction) is performed. After that, you may perform the cyclization condensation reaction which used the devolatilization process simultaneously.

  The devolatilization step is not limited to being completed at the same time as the cyclization condensation reaction, and may be completed after a lapse of time from the completion of the cyclization condensation reaction.

  As described above, the lactone ring-containing polymer preferably uses a catalyst in the cyclization condensation reaction. However, if the catalyst remains in the resin, it is unreacted when the resin is heated. Foaming phenomenon occurs when an alcohol is generated by transesterification of an alkyl ester group with a hydroxyl group of a ring-forming unit (that is, a unit that has not yet formed a ring) or active hydrogen such as water present in a small amount in the system. May happen. In order to prevent this foaming phenomenon, it is preferable to add a deactivator.

  In general, when the catalyst used in the cyclization condensation reaction is an acidic substance, the catalyst remaining after the reaction may be neutralized using a basic substance. Therefore, when the catalyst used for the cyclization condensation reaction is an acidic substance, a basic substance is preferably used as the deactivator. The basic substance is not particularly limited as long as no substance or the like that inhibits the physical properties of the resin composition is generated during heat processing. For example, a metal carboxylate, a metal complex, a metal oxide, etc. can be mentioned.

<Deactivator>
For example, when a lactone ring-containing polymer is used as the methacrylic acid-based resin, as described above, in the lactone cyclization condensation step, a hydroxyl group and an ester group present in the molecular chain of the polymer are cyclized and condensed. A lactone ring structure is formed in the molecular chain of the polymer (in the main skeleton of the polymer) by causing a dealcoholization reaction which is a kind of transesterification. In general, when the catalyst used for transesterification is an acidic substance, the catalyst remaining after the reaction can be deactivated by neutralization with a basic substance.

  Therefore, the quenching agent used in this case is not particularly limited as long as it is a basic substance and does not generate a substance that inhibits the resin composition during heat processing. And metal compounds such as metal complexes and metal oxides.

  Here, the metal constituting the metal compound is not particularly limited as long as it does not inhibit the physical properties of the resin composition and does not cause environmental pollution at the time of disposal. For example, lithium, sodium and potassium Alkaline earth metals such as magnesium, calcium, strontium and barium; amphoteric substances such as zinc, aluminum, tin and lead; zirconium; and the like.

  Of these metals, typical metal elements are preferred because of less coloring of the resin, alkaline earth metals and amphoteric metals are particularly preferred, and calcium, magnesium and zinc are most preferred. The metal salt is preferably an organic acid metal salt, particularly preferably an organic carboxylic acid, an organic phosphoric acid compound, and an acidic organic sulfur compound, from the viewpoint of dispersibility in a resin and solubility in a solvent. The organic carboxylic acid constituting the metal salt of the organic carboxylic acid is not particularly limited. For example, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, Decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, pehenic acid, tridecanoic acid, pentadecanoic acid, heptadecanoic acid, lactic acid, malic acid, citric acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, Examples include adipic acid.

  The organophosphorus compound constituting the metal salt of organophosphoric acid includes alkyl (aryl) sulfonic acid such as methyl sulfonic acid, ethyl sulfonic acid, and phenyl sulfonic acid (however, these are tautomers) Alkyl (aryl) phosphinic acid) and their monoesters or diesters; Dialkyl (aryl) phosphinic acids such as dimethylphosphinic acid, diesterphosphinic acid, diphenylphosphinic acid, phenylmethylphosphinic acid, phenylethylphosphinic acid And alkyl (aryl) phosphonic acids such as methylphosphonic acid, ethylphosphonic acid, trifluoromethylphosphonic acid, phenylphosphonic acid, and monoesters or diesters thereof; methylphosphinic acid, Alkyl (aryl) phosphinic acids such as finic acid and phenylphosphinic acid and esters thereof; methyl phosphite, ethyl phosphite, phenyl phosphite, dimethyl phosphite, diethyl phosphite, diphenyl phosphite Phosphoric acid monoesters, diesters or triesters such as trimethyl phosphite and triethyl phosphite; methyl phosphate, ethyl phosphate, 2-ethylhexyl phosphate, octyl phosphate, isodecyl phosphate, lauryl phosphate, phosphorus Stearyl acid, isostearyl phosphate, phenyl phosphate, dimethyl phosphate, diethyl phosphate, di-2-ethylhexyl phosphate, diisodecyl phosphate, dilauryl phosphate, distearyl phosphate, diisostearyl phosphate, diphenyl phosphate , Trimethyl phosphate, triethyl phosphate, phosphate Phosphoric monoesters, diesters or triesters such as isodecyl, trilauryl phosphate, tristearyl phosphate, triisostearyl phosphate, triphenyl phosphate; methylphosphine, ethylphosphine, phenylphosphine, dimethylphosphine, diethylphosphine, diphenylphosphine Mono-, di- or tri-alkyl (aryl) phosphine such as trimethylphosphine, triethylphosphine, triphenylphosphine; methyldichlorophosphine, ethyldichlorophosphine, phenyldichlorophosphine, dimethylchlorophosphine, diethylchlorophosphine, diphenylchlorophosphine, etc. Alkyl (aryl) halogen phosphines; methyl phosphine oxide, ethyl phosphine oxide, phenyl phosphine oxide Di-, dimethyl phosphine oxide, diethyl phosphine oxide, diphenyl phosphine oxide, trimethyl phosphine oxide, triethyl phosphine oxide, triphenyl phosphine oxide, mono-, di- or tri-alkyl (aryl) phosphine oxides; tetramethylphosphonium chloride, chloride And halogenated tetraalkyl (aryl) phosphoniums such as tetraethylphosphonium and tetraphenylphosphonium chloride.

  Examples of the acidic organic sulfur compound constituting the metal salt of the acidic organic sulfur compound include p-toluenesulfonic acid, methanesulfonic acid, benzenesulfonic acid, xylenesulfonic acid, and dodecylbenzenesulfonic acid. The organic component in the metal complex is not particularly limited, and examples thereof include acetylacetone.

  On the other hand, when the catalyst used for transesterification is a basic substance, for example, an acidic substance such as an organic phosphate compound may be used to deactivate the catalyst remaining after the reaction. In any case, these deactivators may be used alone or in combination of two or more. The quenching agent may be added in any form such as a solid, powder, granule, dispersion, suspension, and aqueous solution, and is not particularly limited.

  On the other hand, when the catalyst used for transesterification is a basic substance, for example, an acidic substance such as an organic phosphorus compound may be used to deactivate the catalyst remaining after the reaction. In any case, these deactivators may be used alone or in combination of two or more. The quenching agent may be added in any form such as a solid, powder, granule, dispersion, suspension, aqueous solution, etc. The form is not particularly limited.

  What is necessary is just to adjust suitably the compounding quantity of a quencher according to the usage-amount of the catalyst used for the cyclization condensation reaction, and it is not specifically limited. For example, based on the mass of the lactone ring-containing polymer, it is preferably 10 ppm to 10,000 ppm, more preferably 50 ppm to 5000 ppm, and still more preferably 100 ppm to 3000 ppm. When the blending amount is less than 10 ppm, the action of the deactivator becomes insufficient, and bubbles may be generated during heating, which is not preferable. If the blending amount exceeds 10,000 ppm, the action of the deactivator is saturated, and the deactivator is used more than necessary, which is not preferable because the production cost may increase.

  The deactivator may be added at any time after the lactone ring structure is formed. For example, after the lactone ring-containing polymer is added at a predetermined stage during the production of the lactone ring-containing polymer to obtain the lactone ring-containing polymer, the lactone ring-containing polymer, the deactivator, and other components are simultaneously heated and melted and kneaded. A method of producing a lactone ring-containing polymer, adding a deactivator, and simultaneously melting and kneading the lactone ring-containing polymer, the deactivator, and other components; kneading; a lactone ring-containing polymer and the like And the like, and a method of kneading them by adding a deactivator, other components, and the like.

  The lactone ring-containing polymer has a weight average molecular weight of preferably 1,000 or more and 2,000,000 or less, more preferably 5,000 or more and 1,000,000 or less, and further preferably 10,000 or more and 500,000 or less. Especially preferably, it is 50,000 or more and 500,000 or less.

  The lactone ring-containing polymer preferably has a weight loss rate of 150% to 300 ° C. in dynamic TG measurement of 1% or less, more preferably 0.5% or less, and still more preferably 0.3% or less. It is.

  Since the lactone ring-containing polymer has a high cyclization condensation reaction rate, it is possible to avoid the disadvantage that bubbles and silver streaks enter the molded product after molding. Furthermore, since the lactone ring structure is sufficiently introduced into the polymer due to a high cyclization condensation reaction rate, the obtained lactone ring-containing polymer has sufficiently high heat resistance.

  The lactone ring-containing polymer preferably has a 5% weight loss temperature in thermogravimetric analysis (TG) of 280 ° C or higher, more preferably 290 ° C or higher, and further preferably 300 ° C or higher. The 5% weight loss temperature in thermogravimetric analysis (TG) is an index of thermal stability, and if it is less than 280 ° C., sufficient thermal stability may not be exhibited.

  The total amount of residual volatile components contained in the lactone ring-containing polymer is preferably 5000 ppm or less, more preferably 2000 ppm or less. When the total amount of residual volatile components is more than 5000 ppm, coloring due to deterioration during molding, foaming, and molding defects such as silver streak are caused.

  The lactone ring-containing polymer preferably has a total light transmittance of 85% or more, more preferably 88% or more, and still more preferably a molded product obtained by injection molding, as measured by a method according to ASTM-D-1003. Is 90% or more. The total light transmittance is a measure of transparency, and if it is less than 85%, the transparency is lowered and there is a possibility that it cannot be used for the intended purpose.

(3. Physical properties of laminated substrate)
Although the shape of the base material used for the laminated body of this invention is not specifically limited, A film is demonstrated as an example. In addition, a lens, a package, a fiber etc. are mentioned as a shape of a laminated body base material. The laminated substrate film of the present invention has a glass transition temperature of 110 ° C. or more and 200 ° C. or less, and a viscosity at a resin temperature of 270 ° C. when the shear rate is 100 (1 / s) is 250 Pa · s or more and 1000 Pa. -It is preferable to provide acrylic resin which is s or less.

  Substances that can become glass are generally in a low-temperature glass state and in a high-temperature supercooled liquid state, with a narrow temperature range inherent to the substance as a boundary, thermal expansion coefficient, electrical conductivity, viscosity, etc. The temperature coefficient and other physical quantities of the abruptly change. The glass transition temperature refers to the temperature range at this boundary, and is the temperature at which the polymer begins micro-Brownian motion.

  Although there are various measuring methods for the glass transition temperature, in this specification, it is defined as a temperature obtained by a midpoint method according to ASTM-D-3418 using a differential scanning calorimeter (DSC). The laminate base material of the present invention includes an acrylic resin having a glass transition temperature of 110 ° C. or higher and 200 ° C. or lower, and the acrylic resin is generally recognized as a heat-resistant acrylic resin among the traders.

  When the glass transition temperature is higher than 200 ° C., the fluidity of the molten resin is deteriorated, so that it is difficult to form a film. The glass transition temperature is preferably 115 ° C. or higher and 180 ° C. or lower, more preferably 120 ° C. or higher and 160 ° C. or lower.

  The acrylic resin is required to have a viscosity of 250 Pa · s or more and 1000 Pa · s or less at a resin temperature of 270 ° C. when the shear rate is 100 (1 / s). The shear rate refers to a change in flow velocity based on a difference in position in a direction perpendicular to the wall surface when the fluid flow is along the wall. The shear rate usually takes the maximum value on the wall surface and decreases as the distance from the wall surface increases. The shear rate of 100 (1 / s) is the central value of the speed that normally acts in the extruder.

  The acrylic resin preferably has a viscosity of 300 Pa · s to 2000 Pa · s when the resin temperature is 250 ° C. when the shear rate is 100 (1 / s).

  Moreover, it does not specifically limit as a method to measure the said viscosity, It can measure using a conventionally well-known rheometer etc.

  The film concerning this invention is equipped with the said acrylic resin. Examples of components other than the acrylic resin include polymers other than acrylic resins (other polymers), other additives, and the like.

  Examples of other polymers include olefin polymers such as polyethylene, polypropylene, ethylene-propylene copolymer, poly (4-methyl-1-pentene); halogen-containing polymers such as vinyl chloride and vinyl chloride resin; Acrylic polymers such as methyl methacrylate; Styrene polymers such as polystyrene, styrene-methyl methacrylate copolymer, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene block copolymer; polyethylene terephthalate, polybutylene terephthalate, polyethylene Polyester such as naphthalate; Polyamide such as nylon 6, nylon 66, nylon 610; Polyacetal; Polycarbonate; Polyphenylene oxide; Polyphenylene sulfide; Teruketon; polysulfone; polyether sulfone; polyoxyethylene benzylidene alkylene; polyamideimide; polybutadiene rubber, rubber-like polymer such as ABS resin or ASA resin containing an acrylic rubber; and the like.

  The content of the other polymer in the film is preferably 0% by weight to 50% by weight, more preferably 0% by weight to 40% by weight, further preferably 0% by weight to 30% by weight, particularly preferably. It is 0 to 20% by weight.

  Examples of the other additives include antioxidants such as hindered phenols, phosphorus, and sulfur; stabilizers such as light stabilizers, weather stabilizers, and heat stabilizers; reinforcements such as glass fibers and carbon fibers. Materials: UV absorbers such as phenenyl salicylate, (2,2'-hydroxy-5-methylphenyl) benzotriazole, 2-hydroxybenzophenone; near infrared absorbers; tris (dibromopropyl) phosphate, triallyl Flame retardants such as phosphate and antimony oxide; Antistatic agents such as anionic, cationic and nonionic surfactants; Colorants such as inorganic pigments, organic pigments and dyes; Organic fillers and inorganic fillers; Resin modifiers; Organic fillers and inorganic fillers; plasticizers; lubricants; antistatic agents; flame retardants;

  The content of the other additives in the film is preferably 0% by weight to 5% by weight, more preferably 0% by weight to 2% by weight, and further preferably 0% by weight to 0.5% by weight. .

  The other polymers and additives are preferably melt kneaded with an acrylic resin in advance before film formation.

≪Resin composition≫
The resin composition used in the present invention contains a ketone solvent and a vinyl compound.

<Ketone solvent>
Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketone, methyl butyl ketone, methyl isobutyl ketone, methyl tertiary butyl ketone, cyclohexanone, and the like. Particularly, methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketone, Methyl isobutyl ketone and cyclohexanone are preferred.

  The boiling point of the ketone solvent in the resin composition of the present invention is preferably 200 ° C. or less, more preferably 150 ° C. or less, and particularly preferably 130 ° C. or less. Moreover, it is preferable that it is 40 degreeC or more. When the boiling point is too high, when the composition is air-dried, it may take a long time to dry and the productivity may deteriorate. If the boiling point is too low, there is a risk of solvent contamination in the working environment, which is not preferable. In the present application, a reactive diluent having a ketone group is also included as a ketone solvent.

  The ketone solvent in the resin composition is preferably 50% or more, more preferably 75% or more. When it is less than 50%, the substrate adhesion may be deteriorated. The upper limit is preferably 95% or less, and more preferably 90% or less. When the amount of the ketone solvent is more than 95%, the amount of the vinyl compound is relatively small, which is not preferable.

<Vinyl compound (A)>
The vinyl compound in the present invention is not particularly limited as long as it is a conventionally known compound having a polymerizable unsaturated group.

  Preferably the following formula (1):

[Wherein R ¹ is an alkylene group having 2 to 8 carbon atoms, R ² is a hydrogen atom or a methyl group, and m is a positive integer]
It is a case where the vinyl polymer (A) which has a repeating unit shown by is contained.

  In the resin composition of the present invention, the amount of the vinyl polymer represented by the formula (1) is preferably 10 to 100% by mass, more preferably 20 to 90% by mass, based on the total amount of the composition. More preferably, it is 20 to 80% by mass. When the blending amount of the vinyl polymer is less than 10% by mass, the crosslinking density is lowered, so that the curing rate is lowered and the coating strength of the cured product may be insufficient.

  In the vinyl polymer represented by the above formula (1), when the low molecular weight component is increased, the strength and hardness of the cured film layer may be decreased. The number average molecular weight (Mn) of the vinyl polymer is preferably in the range of 3000 to 50,000, more preferably 4000 to 30,000, and still more preferably 5000 to 20,000. When the number average molecular weight (Mn) of the vinyl polymer is less than 3000, the curing rate may be decreased and the strength of the cured product may be decreased. Further, if it exceeds 50,000 (the numerical value has been changed), the wettability with the base material decreases and the viscosity increases. For example, when adjusting the resin composition, the mixing time becomes longer, or the coating property is increased. The workability such as the above may be deteriorated.

  The vinyl polymer represented by the above formula (1) can be obtained as a liquid viscous material except in the case of a polymer having a high solid monomer content. If it is a liquid viscous body, since the solubility with an organic solvent or a (meth) acrylate type monomer is good, improvement in work efficiency can be achieved when adjusting a resin composition. When the viscosity is low, workability is good, and wettability with the base material is improved when a laminate is produced.

In the above formula (1), examples of the alkylene group having 2 to 8 carbon atoms represented by R ¹ include an ethylene group, a trimethylene group, a propylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, and a heptamethylene group. , Octamethylene group, cyclohexylene group, 1,4-dimethylcyclohexane-α, α′-diyl group, 1,3-dimethylcyclohexane-α, α′-diyl group, 1,2-dimethylcyclohexane-α, α ′ -Diyl group, 1,4-dimethylphenyl-α, α'-diyl group, 1,3-dimethylphenyl-α, α'-diyl group, 1,2-dimethylphenyl-α, α'-diyl group, etc. Can be mentioned. There are m substituents represented by R ¹ in the above formula (1), but they may be the same or different.

  In the above formula (1), m is a positive integer, preferably an integer of 1 to 20, more preferably an integer of 1 to 10, more preferably an integer of 1 to 5, and n is a positive integer, preferably 50. An integer of ˜400, more preferably an integer of 100 to 300, and even more preferably an integer of 150 to 250.

<Preparation of vinyl polymer>
The vinyl polymer represented by the above formula (1) has the following formula (2):

[Wherein R ¹ , R ² and m are as defined in the above formula (1)]
Can be prepared by conventionally known cationic polymerization, or by living cationic polymerization by the method described in JP-A-2006-241189. It can also be easily prepared. At this time, the different polymerizable monomers represented by the above formula (2) may be used alone or in combination of two or more. In the latter case, the resulting copolymer may be a random copolymer, an alternating copolymer, a periodic copolymer, a block copolymer, or a combination thereof. Moreover, a graft copolymer may be sufficient.

  Specific examples of the heteropolymerizable monomer represented by the above formula (2) include, for example, 2-vinyloxyethyl (meth) acrylate, 3-vinyloxypropyl (meth) acrylate, and 2-vinyloxy (meth) acrylate. Roxypropyl, 1-vinyloxypropyl (meth) acrylate, 1-methyl-2-vinyloxyethyl (meth) acrylate, 4-vinyloxybutyl (meth) acrylate, 3-vinyloxybutyl (meth) acrylate, (meth) acrylic acid 2-vinyloxybutyl, 1-methyl-3-vinyloxypropyl (meth) acrylate, 2-methyl-3-vinyloxypropyl (meth) acrylate, 1-methyl-2-vinyloxypropyl (meth) acrylate, ( 1,1-dimethyl-2-vinyloxyethyl (meth) acrylate, 6-vinyloxyhexyl (meth) acrylate, ( T) 4-vinyloxycyclohexyl acrylate, 4-vinyloxymethylcyclohexylmethyl (meth) acrylate, 3-vinyloxymethylcyclohexylmethyl (meth) acrylate, 2-vinyloxymethylcyclohexylmethyl (meth) acrylate, ( 4-vinyloxymethylphenylmethyl (meth) acrylate, 3-vinyloxymethylphenylmethyl (meth) acrylate, 2-vinyloxymethylphenylmethyl (meth) acrylate, 2- (2-vinyloxy) (meth) acrylate Ethoxy) ethyl, 2- (2-vinyloxyisopropoxy) ethyl (meth) acrylate, 2- (2-vinyloxyethoxy) propyl (meth) acrylate, 2- (2-vinyloxyiso) (meth) acrylate Propoxy) propyl, (meth) acrylic acid 2- (2-vinyloxy) Toxi) isopropyl, (meth) acrylic acid 2- (2-vinyloxyisopropoxy) isopropyl, (meth) acrylic acid 2- {2- (2-vinyloxyethoxy) ethoxy} ethyl, (meth) acrylic acid 2- { 2- (2-vinyloxyisopropoxy) ethoxy} ethyl, 2- (2- (2-vinyloxyisopropoxy) isopropoxy} ethyl (meth) acrylate, 2- (2- (2- (2- Vinyloxyethoxy) ethoxy} propyl, 2- (2- (2-vinyloxyethoxy) isopropoxy} propyl (meth) acrylate, 2- {2- (2-vinyloxyisopropoxy) ethoxy} (meth) acrylate} Propyl, (meth) acrylic acid 2- {2- (2-vinyloxyisopropoxy) isopropoxy} propyl, (meth) acrylic acid 2- {2- (2-vinyloxyethoxy) ethoxy} isopropyl, (meth) acrylic acid 2- {2- (2-vinyloxyethoxy) isopropoxy} isopropyl, (meth) acrylic acid 2- {2- (2-vinyl) Loxyisopropoxy) ethoxy} isopropyl, 2- {2- (2-vinyloxyisopropoxy) isopropoxy} isopropyl (meth) acrylate, 2- [2- {2- (2-vinyloxyethoxy) (meth) acrylate ) Ethoxy} ethoxy] ethyl, 2- (2- {2- (2-vinyloxyisopropoxy) ethoxy} ethoxy] ethyl (meth) acrylate, 2- (2- [2- {2- (2-vinyloxyethoxy) ethoxy} ethoxy] ethoxy) ethyl; and the like. Among these different polymerizable monomers, 2-vinyloxyethyl (meth) acrylate, 3-vinyloxyethyl (meth) acrylate, 2-vinyloxypropyl (meth) acrylate, 1-methyl-2 (meth) acrylate -Vinyloxyethyl, 4-vinyloxybutyl (meth) acrylate, 6-vinyloxyhexyl (meth) acrylate, 4-vinyloxycyclohexyl (meth) acrylate, 4-vinyloxymethylcyclohexylmethyl (meth) acrylate, (meth) 2- (2-vinyloxyethoxy) ethyl acrylate, 2- (2-vinyloxyisopropoxy) propyl (meth) acrylate, 2- {2- (2-vinyloxyethoxy) ethoxy} ethyl (meth) acrylate Is preferred.

The different polymerizable monomer represented by the above formula (2) can be produced using a conventionally known method. For example, in the above formula (2), when R ¹ is an ethylene group and m is 1, a metal salt of (meth) acrylic acid and 2-halogenoethyl vinyl ether are condensed, or methyl (meth) acrylate and , 2-hydroxyethyl vinyl ether can be transesterified, or (meth) acrylic acid halide and 2-hydroxyethyl vinyl ether can be condensed. In the above formula (2), when R ¹ is an ethylene group and m is 2, a metal salt of (meth) acrylic acid and 2- (2-halogenoethoxy) ethyl vinyl ether are condensed or (meta ) By transesterifying methyl acrylate with 2- (2-hydroxyethoxy) ethyl vinyl ether or condensing (meth) acrylic acid halide with 2- (2-hydroxyethoxy) ethyl vinyl ether, Can be manufactured.

  When the vinyl polymer represented by the above formula (1) is a copolymer having a structural unit derived from a cationically polymerizable monomer, the copolymer is a heteropolymer represented by the above formula (2). It can be easily prepared by cationic polymerization or living cationic polymerization of a cationic monomer and a monomer capable of cationic polymerization. At this time, the different polymerizable monomers represented by the above formula (2) may be used alone or in combination of two or more. The resulting copolymer may be a random copolymer, an alternating copolymer, a periodic copolymer, a block copolymer, or a combination thereof. Moreover, a graft copolymer may be sufficient.

  Examples of the monomer capable of cationic polymerization include methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, t-butyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, octadecyl vinyl ether, Vinyl ether compounds such as 2-chloroethyl vinyl ether, 4-hydroxybutyl vinyl ether, dihydrofuran; styrene, 4-methylstyrene, 3-methylstyrene, 2-methylstyrene, 2,5-dimethylstyrene, 2,4-dimethylstyrene, 2,4,6-trimethylstyrene, 4-t-butylstyrene, 2-chlorostyrene, 3-chlorostyrene, 4-chlorostyrene, 4-methyl Styrene derivatives such as xylstyrene and 4-chloromethylstyrene; N-vinyl compounds such as N-vinylcarbazole and N-vinylpyrrolidone; divinyl compounds such as isopropenylstyrene, 2-vinyloxyethyl cinnamate, 2-vinyloxyethyl sorbate, and trivinyl Compound; and the like. These cationically polymerizable monomers may be used alone or in combination of two or more. Of these cationically polymerizable monomers, vinyl ether compounds such as isobutyl vinyl ether, cyclohexyl vinyl ether, and dihydrofuran are preferable.

  The heterogeneous polymerizable monomer represented by the above formula (2) has a radically polymerizable or anionically polymerizable (meth) acryloyl group and a cationically polymerizable vinyl ether group at the same time. , A polymer having a (meth) acryloyl group or a vinyl ether group as a pendant group is obtained. In the present invention, the vinyl ether group of the heteropolymerizable monomer represented by the above formula (2) is subjected to cationic polymerization or living cationic polymerization alone or together with a monomer capable of cationic polymerization, so that (meth) A vinyl polymer represented by the above formula (1) having an acryloyl group as a pendant group is obtained.

  When the heteropolymerizable monomer represented by the above formula (2) and the cationic polymerizable monomer are subjected to cationic polymerization or living cationic polymerization, the molar ratio of the monomers (cation polymerizable monomer / above The heteropolymerizable monomer represented by the formula (2) is preferably in the range of 0.1 to 10, more preferably 0.5 to 8, and still more preferably 0.8 to 5.

<Modification of vinyl polymer with secondary amine>
A secondary amine may be added to a part of the carbon-carbon double bond of the vinyl polymer represented by the formula (1) to form an amine-modified vinyl polymer. By adding a secondary amine, the polarity of the vinyl polymer having a repeating structural unit represented by the above formula (1) can be increased.
Examples of the secondary amine added to the vinyl polymer having a repeating structural unit represented by the above formula (1) include dimethylamine, diethylamine, di-n-propylamine, di-2-ethylhexylamine, and diisopropyl. Alkylamines and dialkylamines such as amine, dibutylamine, methyloctylamine, methylethylamine, methylpropylamine, and ethylpropylamine; arylamines such as N-methylaniline; diarylamines such as diphenylamine; N-methylethanolamine, N- Hydroxyl group-containing amines such as ethylethanolamine, diethanolamine and diisopropanolamine; halogenated alkylamines such as bis (2-chloroethyl) amine and 2-chloroethyl (propyl) amine; piperidine, - methylpiperidine, 1-methylpiperazine, morpholine, and the like secondary cyclic amines, such as. Among these, dialkylamines such as diisopropylamine and dibutylamine; hydroxyl group-containing dialkylamines such as diethanolamine and diisopropanolamine are preferable.

<Ingredients other than vinyl polymer>
The resin composition used in the present invention may contain polymerizable monomer polymerization and / or an initiator in addition to the vinyl polymer. When a polymerizable monomer is included, the physical properties of a cured product obtained by curing can be adjusted.

  The polymerizable monomer is not particularly limited as long as it can be co-cured with the vinyl polymer represented by the above formula (1). Specific examples thereof include styrene and vinyl toluene. Styrene monomers such as 4-t-butylstyrene, α-methylstyrene, 4-chlorostyrene, 4-methylstyrene, 4-chloromethylstyrene, divinylbenzene; diallyl phthalate, diallyl isophthalate, triallyl cyanurate , Allyl ester monomers such as triallyl isocyanurate; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate , Isobornyl (meth) acrylate, 1-adaman (Meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono ( Monofunctional (meth) acrylates such as (meth) acrylate, methoxydiethylene glycol (meth) acrylate, butoxydiethylene glycol (meth) acrylate, phenoxyethyl (meth) acrylate, trifluoroethyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, etc. Compound; ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) ) Acrylate, 1,9-nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, 2-butyl-2-ethyl-1, 3-propanediol di (meth) acrylate, dimethylol-tricyclodecane di (meth) acrylate, pentacyclopentadecane dimethanol di (meth) acrylate, di (meth) acrylic acid adduct of bisphenol A diglycidyl ether, cyclohexanedimethanol Di (meth) acrylate, norbornane dimethanol di (meth) acrylate, p-menthane-1,8-diol di (meth) acrylate, p-menthan-2,8-diol di (meth) acrylate, p-menthane-3,8- Diol Di (Meta Bifunctional (meth) acrylate compounds such as acrylate, bicyclo [2.2.2] -octane-1-methyl-4-isopropyl-5,6-dimethyloldi (meth) acrylate, and the like; trimethylolpropane tri (meth) acrylate, (Meth) acrylic such as tri- or more functional (meth) acrylate compounds such as trimethylolethane tri (meth) acrylate, glycerin tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. Acid derivatives: methoxyethyl (meth) acrylate, 2-methoxy-2-methylethyl (meth) acrylate, 2-methoxy-1-methylethyl (meth) acrylate, ethoxyethyl (meth) acrylate, 2-ethoxy-2-methyl Chill (meth) acrylate, 2-ethoxy-1-methylethyl (meth) acrylate, propoxyethyl (meth) acrylate, propoxypropyl (meth) acrylate, isopropoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, (meth) acrylic acid 2 -Ethylene oxide addition of vinyloxyethyl, 2- (2-vinyloxyethoxy) ethyl (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, trimethylolpropane (Meth) acrylic derivatives having an ether structure, such as tri (meth) acrylates of products and di (meth) acrylates of ethylene oxide adducts of bisphenol A; Vinyl ether monomers such as lenglycol divinyl ether, cyclohexanedimethanol divinyl ether, hydroxybutyl vinyl ether, dodecyl vinyl ether; trimethylolpropane diallyl ether, pentaerythritol triallyl ether, allyl glycidyl ether, allyl ether of methylol melamine, glyceryl diallyl ether Allyl ether monomers such as adipates, allyl acetals, and allyl ethers of methylol glyoxalurein; maleate esters such as diethyl maleate and dibutyl maleate; dibutyl fumarate, dioctyl fumarate, etc. Fumarate monomer; 4- (meth) acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxola 4- (meth) acryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane, 4- (meth) acryloyloxymethyl-2-cyclohexyl-1,3-dioxolane, 4- (meth) acryloyloxy 1,3-dioxolane monomers such as methyl-2,2-dimethyl-1,3-dioxolane; (meth) acryloylmorpholine; N-vinylformamide; N-vinylpyrrolidone; These polymerizable monomers may be used alone or in combination of two or more. Of these polymerizable monomers, (meth) acrylic ester compounds are preferred, and (meth) acrylic ester compounds having an alicyclic structure substituent and (meth) acrylic derivatives having an ether structure are preferred. is there.

  The compounding amount of the polymerizable monomer is preferably 0 to 80% by mass, more preferably 0 to 60% by mass with respect to the total amount of the composition. When the compounding amount of the polymerizable monomer exceeds 80% by mass, curing shrinkage increases, and internal distortion and warpage of the cured product may increase.

  As the polymerization initiator, since the vinyl polymer represented by the above formula (1) has a radically polymerizable (meth) acryloyl group, for example, a thermal polymerization initiator that generates a polymerization initiating radical by heating; And a photopolymerization initiator that generates a polymerization initiating radical. These polymerization initiators may be used alone or in combination of two or more. It is also preferable to further add a thermal polymerization accelerator, a photosensitizer, a photopolymerization accelerator, and the like.

  Examples of the thermal polymerization initiator include methyl ethyl ketone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide, methyl acetoacetate peroxide, acetyl acetate peroxide, 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1 , 1-bis (t-hexylperoxy) -cyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) -2-methylcyclohexane 1,1-bis (t-butylperoxy) -cyclohexane, 1,1-bis (t-butylperoxy) cyclododecane, 1,1-bis (t-butylperoxy) butane, 2,2-bis (4 4-di-t-butylperoxy Chlohexyl) propane, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-hexyl hydroperoxide, t-butyl hydroperoxide, α, α'- Bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, t-butylcumyl peroxide, di-t-butyl peroxide, 2,5 -Dimethyl-2,5-bis (t-butylperoxy) hexyne-3, isobutyryl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, Succinic acid peroxide, m-toluoyl benzoyl peroxide, benzoyl peroxide, di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, bis (4-tert-butylcyclohexyl) peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate , Di-2-ethoxyhexyl peroxydicarbonate, di-3-methoxybutyl peroxydicarbonate, di-s-butyl peroxydicarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, α, α′- Bis (neodecanoylperoxy) diisopropylbenzene, cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1-cyclohexyl-1-methyl Tylperoxyneodecanoate, t-hexylperoxyneodecanoate, t-butylperoxyneodecanoate, t-hexylperoxypivalate, t-butylperoxypivalate, 1,1,3,3-tetramethylbutyl Peroxy 2-ethylhexanoate, 2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexanoate, 1-cyclohexyl-1-methylethylperoxy 2-ethylhexanoate, t-hexylperoxy- 2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-hexylperoxysopropyl monocarbonate, t-butylperoxysobutyrate, t-butylperoxymalate, t-butylperoxy-3, 5,5-trimethylhexano Tate, t-butylperoxylaurate, t-butylperoxysopropyl monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate, t-butylperoxyacetate, t-butylperoxy-m-toluylbenzoate, t-butylperoxy Benzoate, bis (t-butylperoxy) isophthalate, 2,5-dimethyl-2,5-bis (m-toluylperoxy) hexane, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-bis (benzoyl) Peroxy) hexane, t-butylperoxyallyl monocarbonate, t-butyltrimethylsilyl peroxide, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 2,3-dimethyl-2,3-diphenylbutene Organic peroxide initiators such as tan; 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, 1-[(1-cyano-1-methylethyl) azo] formamide, 1,1′-azobis (Cyclohexane-1-carbonitrile), 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile) ), 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile), 2,2′-azobis (2-methylpropionamidine) dihydrochloride, 2,2′-azobis (2-methyl-) N-phenylpropionamidine) dihydrochloride, 2,2′-azobis [N- (4-chlorophenyl) -2-methylpropionamidine)] dihydrochloride, 2,2′-azobis [N (4-Hydrophenyl) -2-methylpropionamidine)] dihydrochloride, 2,2′-azobis [2-methyl-N- (phenylmethyl) propionamidine] dihydrochloride, 2,2′-azobis [2 -Methyl-N- (2-propenyl) propionamidine] dihydrochloride, 2,2'-azobis [N- (2-hydroxyethyl) -2-methylpropionamidine)] dihydrochloride, 2,2'-azobis [2- (5-Methyl-2-imidazolin-2-yl) propane) dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane) dihydrochloride, 2,2 ′ -Azobis [2- (4,5,6,7-tetrahydro-1H-1,3-diazepin-2-yl) propane) dihydrochloride, 2,2'-azobis [2- (3,4,5, 6-tetrahydropyrimidine- -Yl) propane) dihydrochloride, 2,2'-azobis [2- (5-hydroxy-3,4,5,6-tetrahydropyrimidin-2-yl) propane) dihydrochloride, 2,2'-azobis {2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane} dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane], 2, 2′-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, 2,2′-azobis {2-methyl-N- [1,1-bis (Hydroxymethyl) ethyl] propionamide}, 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2′-azobis (2-methylpropionamide), 2,2 '-Azo Bis (2,4,4-trimethylpentane), 2,2′-azobis (2-methylpropane), 2,2-azobis (2-methylpropionic acid) dimethyl, 4,4′-azobis (4-cyanopentane) Acid) and azo initiators such as 2,2′-azobis [2- (hydroxymethyl) propionitrile]; and the like. These thermal polymerization initiators may be used alone or in combination of two or more. Among these thermal polymerization initiators, radicals can be efficiently generated by the catalytic action of metal soaps such as methyl ethyl ketone peroxide, cyclohexanone peroxide, cumene hydroperoxide, t-butylperoxybenzoate, benzoyl peroxide, and / or amine compounds. Preferred compounds are 2,2′-azobisisobutyronitrile and 2,2′-azobis (2,4-dimethylvaleronitrile).

  Examples of the photopolymerization initiator include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2 -Propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholino Acetophenones such as phenyl) butanone and 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone oligomer; benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether Etc. Zoins; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyl-diphenyl sulfide, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 2 , 4,6-trimethylbenzophenone, 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2-propenyloxy) ethyl] benzenemethananium bromide, (4-benzoylbenzyl) trimethylammonium chloride Benzophenones such as 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2- (3-dimethylamino-2-hydroxy) Thioxanthones such as 3,4-dimethyl -9H- thioxanthone-9-Onmesokurorido; and the like. These photopolymerization initiators may be used alone or in combination of two or more. Of these photopolymerization initiators, acetophenones, benzophenones, and acylphosphine oxides are preferable, and 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-methyl-2-morpholino (4- Thiomethylphenyl) propan-1-one, 1-hydroxycyclohexyl phenyl ketone are particularly preferred.

  The blending amount of the polymerization initiator is preferably 0.05 to 20% by mass, more preferably 0.1 to 15% by mass, and further preferably 0.2 to 10% by mass with respect to the total amount of the composition. . When the blending amount of the polymerization initiator is less than 0.05% by mass, the resin composition may not be sufficiently cured. On the other hand, when the blending amount of the polymerization initiator exceeds 20% by mass, the cured product may have odor or color.

  When a thermal polymerization initiator is used as the polymerization initiator, the thermal polymerization can accelerate the decomposition of the thermal polymerization initiator and effectively generate radicals in order to lower the decomposition temperature of the thermal polymerization initiator. An agent can be used. Examples of the thermal polymerization accelerator include metal soaps such as cobalt, copper, tin, zinc, manganese, iron, zirconium, chromium, vanadium, calcium, and potassium, primary, secondary, tertiary amine compounds, and quaternary ammonium. Examples thereof include salts, thiourea compounds, and ketone compounds. These thermal polymerization accelerators may be used alone or in combination of two or more. Among these thermal polymerization accelerators, cobalt octylate, cobalt naphthenate, copper octylate, copper naphthenate, manganese octylate, manganese naphthenate, dimethylaniline, trietalamine, triethylbenzylammonium chloride, di (2-hydroxy) Ethyl) p-toluidine, ethylenethiourea, acetylacetone, methyl acetoacetate are preferred.

  The blending amount of the thermal polymerization accelerator is preferably 0.001 to 20% by mass, more preferably 0.01 to 10% by mass or more, further preferably 0.05 to 5% by mass, based on the total amount of the composition. Is within the range. When the blending amount of the thermal polymerization accelerator is within such a range, it is preferable from the viewpoints of curability of the composition, physical properties of the cured product, and economical efficiency.

  When using a photopolymerization initiator as a polymerization initiator, it is possible to transfer excitation energy from an excited state generated by photoexcitation to the photopolymerization initiator to promote the decomposition of the photopolymerization initiator and generate radicals effectively. The photosensitizer which can be used can be used. Examples of the photosensitizer include 2-chlorothioxanthone, 2,4-diethylthioxanthone, and 2,4-diisopropylthioxanthone. These photosensitizers may be used alone or in combination of two or more.

  The blending amount of the photosensitizer is preferably 0.05 to 20% by mass, more preferably 0.1 to 15% by mass, and still more preferably 0.2 to 10% by mass with respect to the total amount of the composition. Within range. If the compounding quantity of a photosensitizer is in such a range, it is preferable at the point of sclerosis | hardenability of a composition, the physical property of hardened | cured material, and economical efficiency.

  When a photopolymerization initiator is used as the polymerization initiator, a photopolymerization accelerator capable of promoting the decomposition of the photopolymerization initiator and effectively generating radicals can be used. Examples of the photopolymerization accelerator include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 4-dimethylaminobenzoic acid. Examples include 2-n-butoxyethyl, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4′-dimethylaminobenzophenone, and 4,4′-diethylaminobenzophenone. These photopolymerization accelerators may be used alone or in combination of two or more. Of these photopolymerization accelerators, triethanolamine, methyldiethanolamine, and triisopropanolamine are preferable.

  The blending amount of the photopolymerization accelerator is preferably 0.05 to 20% by mass, more preferably 0.1 to 15% by mass, and still more preferably 0.2 to 10% by mass with respect to the total amount of the composition. Within range. When the blending amount of the photopolymerization accelerator is within such a range, it is preferable from the viewpoint of curability of the composition, physical properties of the cured product, and economic efficiency.

  When blending a combination of a thermal polymerization initiator, a photopolymerization initiator, a thermal polymerization accelerator, a photosensitizer, a photopolymerization accelerator, etc., the total amount of the blending amount is based on the total amount of the resin composition, Preferably it is 0.05-20 mass, More preferably, it is 0.1-15 mass%, More preferably, it exists in the range of 0.2-10 mass. If the total amount of the combination amount such as the polymerization initiator is within such a range, it is preferable in terms of the curability of the resin composition, the physical properties of the cured product, and the economical efficiency.

  In the resin composition used in the present invention, an organic solvent other than the ketone solvent may be used. In the case of containing an organic solvent, it becomes possible to improve the adhesion between the cured film layer and the plastic substrate, and to easily dissolve or disperse a metal oxide or additive described later.

  Examples of the organic solvent used include aromatic hydrocarbons such as benzene, toluene and chlorobenzene; aliphatic or alicyclic hydrocarbons such as pentane, hexane, cyclohexane and heptane; carbon tetrachloride, chloroform and ethylene dichloride. Halogenated hydrocarbons; Nitro compounds such as nitromethane and nitrobenzene; Ethers such as diethyl ether, methyl t-butyl ether, tetrahydrofuran and 1,4-dioxane; Esters such as methyl acetate, ethyl acetate, isopropyl acetate and amyl acetate; Dimethyl Alcohols such as formamide, methanol, ethanol, propanol; and the like can be used.

  The blending amount of the organic solvent other than the ketone solvent is preferably 0 to 50% by mass, more preferably 0 to 25% by mass with respect to the total amount of the organic solvent. If the amount of the solvent other than the ketone-based solvent exceeds 50% by mass, the base material adhesion of the cured product layer is reduced, or time is required for distilling off the solvent from the resin composition. May remain.

  The resin composition used in the present invention may preferably contain fine particles made of a metal oxide in addition to the vinyl polymer. In the case of containing fine particles made of a metal oxide, the hardness of the coating film after curing is improved, and there is an effect that a coating having low reflectivity is obtained with less damage.

More preferably, the metal oxide constituting the fine particles contains at least one metal element selected from the group consisting of Si, Ti, Zr, Zn, Sn, In, La, and Y. The metal oxide constituting the fine particles may be a single oxide containing these elements or a complex oxide containing these elements. Specific examples of the metal oxide constituting the fine particles, for _{example, SiO, SiO 2, TiO 2} , ZrO 2, ZnO, SnO 2, In 2 O 3, La 2 O 3, Y 2 O 3, SiO 2 -Al ₂ O ₃ , SiO ₂ —Zr ₂ O ₃ , SiO ₂ —Ti ₂ O ₃ , Al ₂ O ₃ —ZrO ₂ , TiO ₂ —ZrO _{2 and the} like. The fine particles comprising these metal oxides may be used alone or in combination of two or more. Of these fine particles made of a metal oxide, SiO ₂ , TiO ₂ , ZrO ₂ , and ZnO ₂ are preferable.

  The average particle diameter of the fine particles made of a metal oxide is preferably 1 to 300 nm, more preferably 1 to 50 nm. If the average particle diameter of the fine particles exceeds 300 nm, the transparency of the cured product may be impaired. In addition, the average particle diameter of fine particles means the volume average particle diameter calculated | required by measuring using a dynamic light scattering type particle size distribution measuring apparatus.

  The blending amount of the fine particles composed of the metal oxide is preferably 0 to 80% by mass, more preferably 0 to 50% by mass with respect to the total amount of the composition. If the amount of fine particles exceeds 80% by mass, the cured product may become brittle.

  In the resin composition used in the present invention, as necessary, an inorganic filler, a non-reactive resin and / or a reactive resin (for example, acrylic resin, urethane acrylate resin, polyester resin, polyurethane) Resin, polystyrene resin, polyvinyl chloride resin, etc.), color pigment, plasticizer, chain transfer agent, polymerization inhibitor, ultraviolet absorber, near infrared absorber, light stabilizer, antioxidant, flame retardant, matte Agents, dyes, antifoaming agents, leveling agents, antistatic agents, dispersants, slip agents, surface modifiers, thixotropic agents, thixotropic aids and the like can be added. The presence of these additives does not particularly affect the effects of the present invention. These additives may be used alone or in combination of two or more.

  The blending amount of the additive may be appropriately set according to the type and purpose of use of the additive, the use and usage of the resin composition, and is not particularly limited. For example, the compounding amount of the inorganic filler is preferably in the range of 1 to 80% by mass, more preferably 10 to 60% by mass, and further preferably 20 to 50% by mass with respect to the total amount of the resin composition. . The amount of the non-reactive resin, the color pigment, the plasticizer, or the auxiliary change agent is preferably 1 to 40% by mass, more preferably 5 to 30% by mass, and still more preferably 10 to 10% by mass with respect to the total amount of the composition. It is in the range of 25% by mass. The amount of polymerization inhibitor, UV absorber, antioxidant, matting agent, dye, antifoaming agent, leveling agent, antistatic agent, dispersant, slip agent, surface modifier or auxiliary agent is included in the composition. Preferably it is 0.0001-5 mass% with respect to the total amount of a thing, More preferably, it is 0.001-3 mass%, More preferably, it exists in the range of 0.01-1 mass%.

<< Manufacture and laminate of resin composition >>
The resin composition used in the present invention includes a vinyl polymer represented by the above formula (1), if necessary, a polymerizable monomer and a polymerization initiator, a thermal polymerization accelerator, a photosensitizer, It can be obtained by blending a photopolymerization accelerator and the like, further organic solvent, fine particles of metal oxide, various additives, and the like, and mixing and stirring.

  In the resin composition used in the present invention, when a polymerization initiator is not blended, by irradiation with an electron beam, when a thermal polymerization initiator is blended, by heating, or a photopolymerization initiator. Can be cured by irradiation with ultraviolet rays. The cured product of the present invention is obtained by curing the resin composition. Here, the “cured product” means a substance having no fluidity.

  For example, in the case of curing by heating, infrared rays, far infrared rays, hot air, high frequency heating, or the like may be used. The heating temperature may be appropriately adjusted according to the type of the substrate, and is not particularly limited, but is preferably 80 to 200 ° C, more preferably 90 to 180 ° C, and still more preferably 100 to 170 ° C. Within range. The heating time may be appropriately adjusted according to the application area and the like, and is not particularly limited, but is preferably 1 minute to 24 hours, more preferably 10 minutes to 12 hours, and even more preferably 30 minutes to 6 hours. Is within the range.

For example, in the case of curing with ultraviolet rays, a light source including light within a wavelength range of 150 to 450 nm may be used. Examples of such a light source include sunlight, low-pressure mercury lamp, high-pressure mercury lamp, ultrahigh-pressure mercury lamp, metal halide lamp, gallium lamp, xenon lamp, flash type xenon lamp, and carbon arc lamp. Together with these light sources, it is possible to use heat by infrared rays, far infrared rays, hot air, high-frequency heating or the like. The irradiation integrated light amount is preferably in the range of 0.1 to 5 J / cm ² , more preferably 0.15 to 3 J / cm ² , and still more preferably 0.15 to 1 J / cm ² .

  For example, in the case of curing with an electron beam, an electron beam having an acceleration voltage of preferably 10 to 500 kV, more preferably 20 to 300 kV, and even more preferably 30 to 200 kV may be used. The irradiation amount is preferably in the range of 2 to 500 kGy, more preferably 3 to 300 kGy, and still more preferably 4 to 200 kGy. Along with an electron beam, it is possible to use heat by infrared rays, far infrared rays, hot air, high-frequency heating or the like.

As a coating method when the resin composition used in the present invention is applied to a substrate and cured to obtain a laminate, various printing methods such as gravure printing, bar coater method, spin coater method, brush coating, etc. A conventionally known method such as coating, spray coating or dipping may be selected according to the purpose of use. The coating amount is preferably 0.2 to 100 g / m ² , more preferably 0.5 to 70 g / m ² . Moreover, as application | coating thickness, Preferably it is 1-500 micrometers, More preferably, it exists in the range of 2-200 micrometers.

  Moreover, as a method of forming a cured film layer using the resin composition used in the present invention, there is a simultaneous molding method using a decorative film containing the resin composition. This method is a resin molding in which a decorative film composed of at least a film and a decorative layer is placed in a mold for injection molding, and after closing the mold, a molding resin is injected into a cavity and the molding resin is solidified. A decorative sheet is obtained by integrally bonding a decorative sheet to the surface of the product.

  Depending on the purpose, the laminate includes an antistatic layer, an adhesive layer, an adhesive layer, an easy-adhesion layer, a strain relaxation layer, an antiglare layer (non-glare) layer, a photocatalyst layer and other antifouling layers, and an antireflection layer. In addition, various functional coating layers such as an ultraviolet shielding layer, a heat ray shielding layer, an electromagnetic wave shielding layer, and a gas barrier property may be laminated and applied. Note that the order of stacking the hard coat layer and each layer is not particularly limited, and the stacking method is not particularly limited.

The laminate of the present invention includes optical recording disks, plastic films, OA equipment, mobile phones and other communication equipment, household appliances, automotive interior / exterior parts, furniture exterior members, plastic lenses, cosmetic containers, and beverage containers. It is suitably used in application fields such as displays such as organic EL displays, touch panels such as home appliances, sinks, washstands, and even show windows and window glass. It can be particularly suitably used for optical recording disks and plastic films.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by the following examples, but may be appropriately modified within a range that can meet the purpose described above and below. It is also possible to implement, and they are all included in the technical scope of the present invention.

<Adhesion evaluation>
According to JIS K5400, a grid cut (1 mm × 1 mm, 100 mm) was made on the cured product surface of the laminate, and a peel test using a cellophane adhesive tape was performed. The numerical value is shown by the remaining number.

○: 100 (no peeling)
Δ: 99-95
X: 94-1
XX: 0 (all peeled)
<Scratch resistance>
Using a wear resistance tester (model IMC-154A, manufactured by Imoto Seisakusho Co., Ltd.) on the cured product surface of the laminate, steel wool # 0000 was reciprocated at a reciprocating speed of 30 mm / second, After reciprocating 10 times at a reciprocating distance of 25 mm, the degree of damage was visually observed and evaluated according to the following criteria.

○: No change in load of 200 g / cm ² (no scratches observed)
×: Several scratches are observed at a load of 200 g / cm ² <Pencil hardness>
It measured based on JIS-K5400 using the pencil scratch hardness tester (made by Yasuda Seiki Seisakusyo Co., Ltd.) with respect to the hardened | cured material surface of a laminated body. The load was 1,000 g.

<Warpage amount>
After the laminated body cut out to 15 cm × 15 cm was placed on the upper surface side on the horizontal platform under the condition of temperature 25 ° C., the average value of the floating height from the horizontal platform at the four corners was measured, and the following criteria were used. evaluated.

◎: Less than 3 mm ○: 3 mm or more and less than 8 mm Δ: 8 mm or more and less than 15 mm ×: 15 mm or more <Molecular weight>
Number average molecular weight (Mn), weight average molecular weight (Mw), and molecular weight distribution (Mw / Mn) are columns made by Tosoh Corporation under the conditions of a temperature of 40 ° C. and a flow rate of 0.3 mL / min using THF as a mobile phase. It is the value which calculated | required by the gel permeation chromatography (GPC) apparatus HLC-8220GPC made from Tosoh Corporation using 2 TSK-gel SuperHM-H and 1 TSK-gel SuperH2000, and converted into standard polystyrene. The vinyl polymer and the base heat-resistant acrylic resin were analyzed by the same method.

<Polymerization reaction rate, polymer composition analysis>
The reaction rate during the polymerization reaction and the content of the specific monomer unit in the polymer were determined by gas chromatography (manufactured by Shimadzu Corporation, apparatus name: GC17A) based on the amount of unreacted monomer in the obtained polymerization reaction mixture. ) And measured.

<Dynamic TG>
The polymer (or polymer solution or pellet) is once dissolved or diluted in tetrahydrofuran, poured into excess hexane or methanol for reprecipitation, and the taken out precipitate is vacuum dried (1 mmHg (1.33 hPa), 80 ° C. Volatile components and the like were removed by conducting the reaction for 3 hours or more, and the obtained white solid resin was analyzed by the following method (dynamic TG method).

Measuring apparatus: Thermo Plus2 TG-8120 Dynamic TG (manufactured by Rigaku Corporation)
Measurement conditions: Sample amount 5 to 10 mg
Temperature increase rate: 10 ° C / min
Atmosphere: Nitrogen flow 200ml / min
Method: Step-like isothermal control method (controlled at a weight reduction rate value of 0.005% / sec or less between 60 ° C and 500 ° C)
<Dealcoholization reaction rate and proportion of lactone ring structure>
First, from the polymer composition obtained by polymerization, on the basis of the weight loss that occurs when all the hydroxyl groups are dealcoholated as methanol, before decomposition of the polymer starts at 150 ° C. before the weight reduction starts in dynamic TG measurement. From the weight loss due to the dealcoholization reaction up to 300 ° C., the dealcoholization reaction rate was determined.

That is, in the dynamic TG measurement of a polymer having a lactone ring structure, the weight reduction rate between 150 ° C. and 300 ° C. is measured, and the obtained actual weight reduction rate is defined as (X). On the other hand, from the composition of the polymer, all the hydroxyl groups contained in the polymer composition are involved in the formation of the lactone ring, so that the alcohol is converted into alcohol, and the theoretical weight reduction rate (ie, in the composition) The weight reduction rate calculated on the assumption that a 100% dealcoholization reaction has occurred is defined as (Y). The theoretical weight reduction rate (Y) is more specifically the molar ratio of raw material monomers having a structure (hydroxyl group) involved in the dealcoholization reaction in the polymer, that is, the raw material in the polymer composition. It can be calculated from the monomer content. These values (X, Y) are calculated from the dealcoholization formula:
1- (actual weight reduction rate (X) / theoretical weight reduction rate (Y))
Substituting into, the value is obtained and expressed in% to obtain the dealcoholization reaction rate.

  As an example, the proportion of the lactone ring structure in the pellets obtained in Production Example 1 described below is calculated. When the theoretical weight loss rate (Y) of this polymer was determined, the molecular weight of methanol was 32, the molecular weight of methyl 2- (hydroxymethyl) acrylate was 116, and methyl 2- (hydroxymethyl) acrylate. Since the content (weight ratio) in the polymer is 20% by weight in terms of composition, (32/116) × 20≈5.52%.

  On the other hand, the actual weight loss rate (X) by dynamic TG measurement was 0.15% by weight. When these values are applied to the above-described dealcoholization calculation formula, 1− (0.15 / 5.52) ≈0.973, and the dealcoholization reaction rate is 98.3%.

  Then, the content (weight ratio) in the copolymerization composition of the raw material monomer having a structure (hydroxy group) related to lactone cyclization is assumed as having been subjected to predetermined lactone cyclization corresponding to the dealcoholization reaction rate. By multiplying the dealcoholization reaction rate, the content ratio of the structure of the lactone ring unit can be calculated.

  In the case of Production Example 1, the content of 2- (hydroxymethyl) methyl acrylate in the copolymer was 15.0% by weight, the calculated dealcoholization reaction rate was 97.3% by weight, and the molecular weight was 116- ( Since the formula weight of the lactone cyclized structural unit produced when methyl hydroxymethyl) is condensed with methyl methacrylate is 170, the content of the lactone ring in the copolymer is 28.5 (20. 0 × 0.973 × 170/116) wt%.

<Thermal analysis of resin>
Thermal analysis of the acrylic resin was performed using DSC (manufactured by Rigaku Corporation, apparatus name: DSC-8230) under the conditions of a sample of about 10 mg, a heating rate of 10 ° C./min, and a nitrogen flow of 50 cc / min. . The glass transition temperature (Tg) was determined by the midpoint method according to ASTM-D-3418.

<Melt flow rate>
The melt flow rate was measured at a test temperature of 240 ° C. and a load of 10 kg based on JIS-K7210.

<Melt viscosity>
The melt viscosity of the sufficiently dried acrylic resin pellets was measured using a capillary rheometer RH10 manufactured by Borin Instruments.

<Quantification of MMA residual component in film>
The film was dissolved in dimethylacetamide to prepare a 10% by mass solution, and quantified by gas chromatography using diphenyl carbonate as an internal standard.

<B value>
The b value of the optical film was measured using (Nippon Denshoku color difference meter ND-1001DP).

  The b value is a hue value based on JIS Z8729 and indicates the value of b *, and was obtained as an average value of 10 points measured by overlaying an optical film on a standard white plate.

<Extension>
For the stretching of the film, a corner stretch type biaxial stretching test apparatus X6-S manufactured by Toyo Seiki Seisakusho Co., Ltd. was used.

<Direction of film>
The film was formed with an extruder to obtain a sample of a roll-shaped unstretched film. Regarding the direction of the film, the width direction of the roll was the TD direction, and the long direction (longitudinal direction) was the MD direction.

<Optical characteristics>
The in-plane retardation value and thickness direction retardation per film thickness of 100 μm at a wavelength of 589 nm are the in-film retardation value (Re) and thickness measured using KOBRA-WR manufactured by Oji Scientific Instruments. It calculated from the value of the direction phase difference value (Rth).

  The average refractive index of the film measured with an Abbe refractometer, the film thickness d, the slow axis as the tilt central axis, and the incident angle of 40 ° are input, and the in-plane retardation value (Re) and the thickness direction retardation value ( Rth), a retardation value (Re (40 °)) measured by tilting by 40 ° with the slow axis as the tilt axis, and three-dimensional refractive indexes nx, ny, and nz were obtained.

  The total light transmittance and haze were measured using NDH-1001DP manufactured by Nippon Denshoku Industries Co., Ltd. The refractive index was measured in accordance with JIS K 7142 using a refractometer (manufactured by Atago Co., Ltd., apparatus name: Digital Abbe refractometer DR-M2) with respect to a measurement wavelength of 589 nm.

<Thickness of film>
Measurement was performed using a Digimatic Micrometer (manufactured by Mitutoyo Corporation).
<Flexibility>
The flexibility of the film was tested in two directions: a direction in which the film was stretched and a direction perpendicular to the stretched direction. In the case of a biaxially stretched film, the test was performed in two orthogonal stretching directions. When bent at 180 ° at a bending radius of 1 mm in an atmosphere of 25 ° C. and 65% RH, “○” indicates that no cracks are generated in both directions, “△” indicates that cracks are generated in only one direction, and cracks in both directions. The state where the occurrence of was evaluated as “×”.

<Production Example 1>
A 1 m2 reaction kettle equipped with a stirrer, temperature sensor, cooling pipe, and nitrogen introduction pipe is charged with 136 kg of methyl methacrylate (MMA), 34 kg of methyl 2- (hydroxymethyl) acrylate (MHMA), and 166 kg of toluene. Then, while the temperature was raised to 105 ° C. while refluxing nitrogen and refluxed, 187 g of tertiary amyl peroxyisononanoate (manufactured by Atofina Yoshitomi, trade name: Lupazole 570) was added as a polymerization initiator, and at the same time, 374 g of While a solution comprising a polymerization initiator and 3.6 kg of toluene was added dropwise over 2 hours, solution polymerization was performed under reflux (about 105 to 110 ° C.), followed by further aging for 4 hours.

  170 g of stearyl phosphate / distearyl phosphate mixture (manufactured by Sakai Chemicals, product name: Phoslex A-18) was added to the resulting polymer solution and cyclized under reflux (about 90 to 110 ° C.) for 5 hours. A condensation reaction was performed. Subsequently, the polymer solution obtained by the cyclization condensation reaction was subjected to a vent having a barrel temperature of 250 ° C., a rotation speed of 150 rpm, a degree of vacuum of 13.3 to 400 hPa (10 to 300 mmHg), a rear vent of 1 and a forevent of 4 It is introduced into a type screw twin screw extruder (φ = 42 mm, L / D = 42) at a processing rate of 13 kg / hour in terms of resin amount, and is subjected to cyclization condensation reaction and devolatilization in the extruder and extruded. Thus, a transparent pellet was obtained.

  When the obtained pellet was measured by dynamic TG, a mass decrease of 0.15% by mass was detected. The lactone ring-containing polymer has a weight average molecular weight of 147,000, a melt flow rate of 11.0 g / 10 min, a glass transition temperature of 130 ° C., a viscosity of 270 ° C. and a shear rate of 100 (1 / s) at a viscosity of 470 Pa.・ It was s.

  Next, 90 parts of heat-resistant acrylic resin pellets, AS resin (Stylac AS783 manufactured by Asahi Kasei Chemicals Corporation) 10 using a single screw extruder of L / D = 36 consisting of a full flight type screw having a mixing part of φ50 mm, multi-flight structure. And 0.04 part of zinc acetate were melt-extruded at a cylinder set temperature of 270 ° C. at a processing rate of 50 kg / h to prepare pellets (1A).

  The pellet (1A) was charged into a single screw extruder with a vent having φ65 mm, L / D = 32, and a barrier flight type screw. The temperature of the pellet (1A) was set to around 60 ° C. by blowing dehumidified air heated in a hopper. Further, a nitrogen introduction pipe was provided at the lower part of the hopper, and nitrogen gas was introduced into the extruder. While performing suction at 13 hPa (10 mmHg) from the vent port, the mixture was melt kneaded with a barrier flight type screw. After melt-kneading, the pellet (1A) is passed through a leaf disk filter having a filtration area of 0.75 m2 and a filtration accuracy of 5 μm using a gear pump, and a film (1B) is placed on a 90 ° C. cooling roll from a T-die having a width of 700 mm. Molded. The temperature of the cylinder, gear pump, filter, and T die was set to 265 ° C. The film thickness of the obtained film (1B) was 90 μm. The extrusion rate per unit time was 33 kg / hr, and molding was continued for 3 hours, but no so-called eyes were observed on the lip of the T die.

MMA contained in the obtained film was 530 ppm. MMA contained in the acrylic resin composition as a raw material was 500 ppm, and almost no increase was observed in film molding. Therefore, it can be seen that no degradation has occurred during the production of the film. The appearance of the film was also good. Specifically, the b value was 0.70, and the content of impurities was 4 / m2.

The obtained unstretched film (1B) was cut into a 127 mm square both vertically and horizontally, and set on a chuck of a stretching machine so that the MD direction was the stretching direction. The distance inside the chuck was 110 mm both vertically and horizontally. After preheating at 155 ° C. for 3 minutes, the first uniaxial stretching was performed so that the magnification was 1.8 times in 5 seconds. The lateral direction was not shrunk. After completion of stretching, the sample was immediately taken out and cooled. This film was cut into a 97 mm square both vertically and horizontally and stretched in the second stage. The stretching direction was a direction orthogonal to the first-stage stretching direction. The distance inside the chuck was 80 mm both vertically and horizontally. After preheating at 138 ° C. for 3 minutes, second-stage uniaxial stretching was performed so as to be 2.5 times in 2 minutes and 30 seconds. The lateral direction was not shrunk. When a sample was cut out from the obtained sequentially biaxially stretched film and the optical properties were measured, the in-plane retardation value was 46 nm (115 nm per 100 μm), the thickness direction retardation value was 57 nm (143 nm per 100 μm), all The light transmittance was 93%. Moreover, the thickness of the measured film was 40 micrometers, the glass transition temperature was 134 degreeC, and the determination result of the flexibility was (circle).

<Production Example 2>
The polymerization reaction was carried out in a dry nitrogen atmosphere using a sufficiently dried glass container with a three-way cock. First, 159 mL of sufficiently dried and purified toluene, 5 mL of ethyl acetate, and 5 mL of a 1-isobutoxyethyl acetate 0.2 mol / L toluene solution were added to the glass container at room temperature. Further, 25 mL of a 0.1 mol / L toluene solution of ethylaluminum dichloride was added and mixed, and then allowed to stand for 30 minutes to generate a reaction starting species. Next, after the system was cooled to 0 ° C., 0.2 mol of 2- (2-vinyloxyethoxy) ethyl acrylate (VEEA) precooled to 0 ° C. was added, and tin tetrachloride precooled to 0 ° C. was added. The reaction was started by adding 25 mL of a 0.05 mol / L toluene solution. After polymerization for 14 minutes, methanol was added to stop the reaction. Chloroform was added to the mixed solution after the reaction, and the residue of the polymerization initiator was removed by washing with water. Subsequently, after concentrating with an evaporator, it was made to vacuum-dry and the vinyl polymer (PVEEA) was obtained. The reaction rate of the monomer was found to be 98% by analyzing the mixed solution after stopping the reaction by gas chromatography (GC). Moreover, the number average molecular weight (Mn) of the obtained vinyl polymer was 14,200, and molecular weight distribution (Mw / Mn) was 1.10. Further, when the obtained vinyl polymer was subjected to ¹ H-NMR measurement (measuring solvent: deuterated chloroform, measuring instrument: 400 MHz ¹ H-NMR UNITYplus 400 manufactured by Varian), the acryloyl group remained and was selected. In particular, it was confirmed that the acryloyl group pendant polymer has a vinyl ether group polymerized and has a double bond capable of radical polymerization in the side chain.

<Example 1>
100 parts by mass of vinyl polymer (PVEEA) obtained in Production Example 2, 100 parts of methyl ethyl ketone (MEK), photopolymerization initiator 1-hydroxy-cyclohexyl-phenyl-ketone (trade name “Irgacure 184”, Ciba Specialty A coating solution was prepared by mixing and stirring 3 parts by mass of Chemicals Co., Ltd. and 0.1 part of a surface modifier polyether-modified polydimethylsiloxane (trade name “BYK306”, manufactured by Big Chemie Japan Co., Ltd.).

On the (meth) acrylic resin film containing the lactone ring obtained in Production Example 1, a coating solution was applied using a bar coater # 5. Then, it heat-dried at 80 degreeC for 2 minute (s), MEK was evaporated, and the resin layer (hard-coat layer) was formed. This film was UV-cured using a high-pressure mercury lamp under the conditions of an illuminance of 150 mW / cm 2 and an irradiation integrated light quantity of 300 mJ / cm ² to obtain a film with a hard coat layer (laminate). The thickness of the hard coat layer was measured and found to be 3 μm.

Further, a laminate having a hard coat layer thickness of 10 μm was obtained in the same manner except that the bar coater # 14 was used. Table 1 shows the evaluation of the laminate.

<Examples 2 to 10, Comparative Examples 11 to 14, Reference Example 15>
Using the same apparatus as in Example 1, a laminate was prepared with the composition mixing ratios and raw materials shown in Table 2. The evaluation results are shown in Table 1.

Abbreviations in the table are as follows.

U-15HA, U-6LPA: Shin-Nakamura Chemical hard urethane acrylate DPHA: Dipentaerythritol hexaacrylate TMPTA: Trimethylolpropane triacrylate 3000M: Kyoeisha Chemical hard epoxy acrylate Photoinitiator: 1-hydroxy-cyclohexyl-phenyl- Ketone (trade name “Irgacure 184”, manufactured by Ciba Specialty Chemicals Co., Ltd.)
Surface modifier: polyether-modified polydimethylsiloxane (trade name “BYK306”, manufactured by Big Chemie Japan Co., Ltd.)

Claims (4)

A laminate in which a layer obtained by applying a resin composition containing a ketone solvent and a vinyl compound on the surface of a base material containing a heat-resistant acrylic resin as a main component is formed. The laminate according to claim 1, wherein the content of the ketone solvent is 50% by mass or more as the solvent. As a vinyl compound, the following formula (1):

[Wherein R ¹ is an alkylene group having 2 to 8 carbon atoms, R ² is a hydrogen atom or a methyl group, and m is a positive integer]
The laminated body in any one of Claim 1 or 2 containing the vinyl polymer which has a repeating unit shown by these. The image display apparatus obtained using the laminated body in any one of Claims 1-3.