JP2008291198A - Acrylic resin composition and molded article from the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an acrylic resin composition and a molded article from the same being improved in moisture absorbing properties and molding shrinkage without imparing excellent transparency and weatherability which are inherent in the acrylic resin. <P>SOLUTION: An acrylic resin composition having methyl (meth)acrylate as a main ingredient unit is provided. The composition comprises a terpene-based (meth)acrylate ester derived by an esterification reaction of a 12-26C alicyclic hydroxy compound with a (meth)acrylic acid compound and having ≥11.0 difference of contribution degree of Hansen solubility parameters calculated by bringing butyl acrylate as the datum point. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an acrylic resin composition containing a terpene (meth) acrylic acid ester as a monomer component and a molded product thereof.

  Acrylic resins have properties balanced in mechanical strength, molding processability, weather resistance, and the like, and are used in various fields as sheet materials or molding materials. Furthermore, the acrylic resin has optically excellent characteristics such as high transparency, high Abbe number, and low birefringence. Recently, taking advantage of these characteristics, disk materials such as video discs, audio discs and write-once discs for computers, lens materials for cameras, video cameras, projection televisions, optical pickups, etc., as well as various types of light such as optical fibers and optical connectors. Applications are expanding as transmission materials, and IT materials such as light guide plates and light diffusion plates.

  However, acrylic resins have a problem of high hygroscopicity. That is, there is a use in which the use thereof is limited because dimensional changes due to moisture absorption and warping of the molded product may occur, or cracks may occur due to a long cycle of moisture absorption and drying. In particular, it is said that adverse effects of dimensional changes due to moisture absorption are great when used in disk materials, optical pickup lenses, connectors, and the like used in those optical systems. A sheet made of an acrylic resin may be warped due to moisture absorption.

Thus, many proposals have been made regarding techniques for improving the hygroscopicity while maintaining the properties of acrylic resin. For example, as a resin imparted with low water absorption to an acrylic resin, from a low hygroscopic methacrylic resin obtained by copolymerizing a monomer such as isobornyl methacrylate with a methyl methacrylate unit (see Patent Document 1), methacrylic acid ester / isobutene / maleimide A copolymer (see Patent Document 2) is proposed.
JP 60-115605 A Japanese Patent Laid-Open No. 6-136058

  However, the low hygroscopic methacrylic resin of Patent Document 1 does not sufficiently improve the hygroscopicity, and the copolymer of methacrylic acid ester / isobutene / maleimide of Patent Document 2 has a problem that it is colored because it contains a maleimide component. .

Further, the cured product obtained by curing the acrylic resin composition with ultraviolet rays has a problem that the shrinkage is large during the curing process. This causes problems such as warping and distortion when the adherend is thin, and cracks in the cured product. In order to solve this problem, Patent Document 3 proposes a method of adding an acrylic oligomer containing one or more (meth) acryloyl groups to an acrylic resin composition, but shrinkage reduction during curing is not sufficiently improved. .
JP 2006-193660 A

  The present invention has been made against the background of the problems of the prior art. An acrylic resin composition having improved hygroscopicity and cure shrinkage without impairing transparency and weather resistance, which are the characteristics of an acrylic resin, and molding thereof The purpose is to provide a body.

  As a result of diligent studies to solve such problems, in an acrylic resin composition having methyl (meth) acrylate as a main component, an alicyclic hydroxy compound having 12 to 26 carbon atoms having a terpene skeleton and (meta ) By making terpene (meth) acrylic acid ester derived by esterification reaction with acrylic acid compound at least an essential structural unit, it is hygroscopic without impairing transparency and weather resistance, which are the characteristics of acrylic resin. And the cure shrinkage was found to be improved.

  Further, the present invention provides a terpene (meth) acrylic acid ester derived from an esterification reaction of an alicyclic hydroxy compound having 12 to 26 carbon atoms having a terpene skeleton and a (meth) acrylic acid compound. An acrylic resin composition having a Hansen solubility parameter difference of 11.0 or more as a starting point is provided.

  Moreover, this invention provides the acrylic resin composition which makes the monomer component shown to following formula (1) and / or Formula (2) as said terpene type | system | group (meth) acrylic acid ester.

      In the above formula, R1 represents a hydrogen atom or a methyl group.

      In the above formula, R2 represents a hydrogen atom or a methyl group.

  Moreover, this invention provides the molded object which consists of the said acrylic resin composition which can be commercialized with all the shaping | molding methods.

  The acrylic resin composition of the present invention is improved in hygroscopicity and cure shrinkage without impairing the transparency and weather resistance that are the characteristics of the acrylic resin. Therefore, the acrylic resin composition of the present invention and the composition are used. The molded body is optimal for applications in the electronics field, such as disk materials, lens materials, optical transmission materials, and IT materials.

  The acrylic resin composition of the present invention and a molded body using the composition will be described. The acrylic resin composition of the present invention comprises methyl (meth) acrylate as a main unit, and methyl (meth) acrylate includes methyl methacrylate and methyl acrylate. These can be used alone or in combination of two or more. “(Meth) acryl” means “methacryl” or “acryl”.

  The use ratio of methyl (meth) acrylate is desirably 50 to 99.9% by mass, and more desirably 60 to 95% by mass. When the amount is less than 50% by mass, the original properties of the acrylic resin are impaired. When the amount exceeds 99.9% by mass, no effect is obtained in terms of reducing the hygroscopicity or the curing shrinkage. However, the amount used can be appropriately changed and used by blending auxiliary materials such as additives and molding agents depending on the type and application of the objective molded body.

  Moreover, this invention is induced | guided | derived by esterification reaction of a C12-C26 alicyclic hydroxy compound which has a terpene skeleton, and a (meth) acrylic acid compound from a viewpoint of the hygroscopic property of the molded object obtained, and hardening shrinkage. The terpene-based (meth) acrylic acid ester is an acrylic resin composition having at least an essential structural unit, and a molded body using the composition.

  The main component of the acrylic resin composition is a terpene (meth) acrylic acid ester derived from an esterification reaction between an alicyclic hydroxy compound having a terpene skeleton other than 12 to 26 carbon atoms and a (meth) acrylic acid compound. The compatibility with the component unit methyl (meth) acrylate is reduced, and the resulting molded article is not sufficiently effective in reducing hygroscopicity and curing shrinkage.

  Furthermore, in the terpene (meth) acrylic acid ester derived from the esterification reaction of an alicyclic hydroxy compound having 12 to 26 carbon atoms having a terpene skeleton and a (meth) acrylic acid compound, butyl acrylate was used as the origin. It is desirable that the Hansen solubility parameter contribution ratio difference is 11.0 or more, and examples thereof include terpene (meth) acrylic acid esters such as the following formulas (1) to (8). Among these, terpene (meth) acrylic acid esters represented by formula (1) and / or formula (2) are particularly preferable.

      In the above formula, R1 represents a hydrogen atom or a methyl group.

      In the above formula, R2 represents a hydrogen atom or a methyl group.

      In the above formula, R3 represents a hydrogen atom or a methyl group.

      In the above formula, R4 represents a hydrogen atom or a methyl group.

      In the above formula, R5 represents a hydrogen atom or a methyl group.

      In the above formula, R6 represents a hydrogen atom or a methyl group.

      In the above formula, R7 represents a hydrogen atom or a methyl group.

      In the above formula, R8 represents a hydrogen atom or a methyl group.

  The terpene-based (meth) acrylic acid ester of the formula (1) of the present invention shows structural isomers such as the following formulas (9) to (11), but may be used alone or in combination, and is not particularly limited.

      In the above formula, R9 represents a hydrogen atom or a methyl group.

      In the above formula, R10 represents a hydrogen atom or a methyl group.

      In the above formula, R11 represents a hydrogen atom or a methyl group.

Here, the difference in the contribution ratio of the Hansen solubility parameter will be described. The calculation method of the contribution rate difference is described in the second edition (pages 81 to 84) published by Information Technology Corporation, March 31, 2005, Hideki Yamamoto, “SP Value Basics / Applications and Calculation Methods”. .
First, Hansen uses the solubility parameter shown in Equation 1 in consideration of the dispersive force, dipole interaction, and hydrogen bond effects that are involved in the solubility parameter (δ) of Hildebrand. Δ _d (contribution due to dispersion force), δ _p (contribution due to polar interaction), δ _h (contribution due to hydrogen bond) of (meth) acrylic acid ester is calculated, and the solubility of Hansen using Equations 2 to 4 The contribution rate of parameters was calculated. From these values, the distance (contribution rate difference) with butyl acrylate as the origin was determined.

δ _d represents the contribution due to the dispersion force, δ _p represents the contribution due to the polar interaction, and δ _h represents the contribution due to the hydrogen bond.

  The difference in contribution ratio with the origin of butyl acrylate of the terpene-based (meth) acrylate ester represented by the above formula (1) or formula (2) is 14.55 when R1 in formula (1) represents a hydrogen atom, When R1 represents a methyl group, it is 15.47, when R2 of formula (2) represents a hydrogen atom, 14.65, and when R2 represents a methyl group, 15.55, both of which are 11.0 or more It is a value.

For example, when the contribution ratio of butyl acrylate is f _d = 61.05%, f _p = 11.55%, f _h = 27.40%, R1 shown in formula (1) represents a hydrogen atom. The contribution ratio of the terpene (meth) acrylic acid ester is f _d = 72.91%, f _p = 6.26%, f _h = 20.83%, and therefore R1 shown in the formula (1) The distance (contribution rate difference) between the terpene-based (meth) acrylate and butyl acrylate when is a hydrogen atom is ((72.91-61.05) ² + (6.26-11.55) ² + The square root of (20.83 to 27.40) ² ) is 14.55.

  When the difference in contribution ratio to butyl acrylate is less than 11.0, it indicates that the polarity is high, and therefore, the compatibility with methyl (meth) acrylate, which is the main component unit of the acrylic resin composition, is not preferable. . The terpene-based (meth) acrylic acid ester having a contribution difference with respect to butyl acrylate of less than 11.0 includes isobornyl acrylate with a contribution difference of 8.92.

  The number of carbons having a terpene skeleton in the terpene (meth) acrylic acid ester derived from an esterification reaction of an alicyclic hydroxy compound having 12 to 26 carbon atoms having a terpene skeleton and a (meth) acrylic acid compound of the present invention Examples of the alicyclic hydroxy compounds of 12 to 26 include hydrocarbon monoterpenes such as pinene, limonene, terpinene, myrcene, ocimene, dipentene, terpinolene, ferrandlene, silvestrene, sabinene, karen, camphene, tricyclene, and fenchen. Examples of the starting material include those reacted through processes such as an acid catalyst addition reaction, an oxidation reaction, a reduction reaction, and a hydrogenation reaction. Specific examples include those represented by the following formulas (12) to (16).

  The alicyclic hydroxy compound of the formula (12) of the present invention shows structural isomers such as the following formulas (14) to (16), but is not particularly limited.

  (Meth) acrylic acid compounds include (meth) acrylic acid, anhydrous (meth) acrylic acid, (meth) acrylic acid chloride, methyl (meth) acrylate, ethyl (meth) acrylate, allyl (meth) acrylate, (Meth) vinyl acrylate, (meth) isopropyl isopropyl, (meth) propyl acrylate, (meth) butyl acrylate, (meth) acrylate isobutyl, (meth) acrylate 2-ethylhexyl, (meth) acrylate cyclohexyl And (meth) acrylic acid hexyl and the like, and (meth) acrylic acid, (meth) acrylic acid chloride, methyl (meth) acrylate, and ethyl (meth) acrylate are preferably used.

The esterification method of a C12-C26 alicyclic hydroxy compound having a terpene skeleton and a (meth) acrylic acid compound is, for example, an alicyclic hydroxy compound of the above formula (12) or formula (13) and (meth). It can be produced by a conventional esterification method such as esterification reaction in the presence of acrylic acid, transesterification reaction using (meth) acrylic acid ester, condensation reaction using (meth) acrylic acid chloride, etc. The method is not particularly limited. Patent Document 4 describes a starting material, a synthesis method, a synthesis rate, and the like for the terpene (meth) acrylic acid ester of formula (1) or formula (2), but is not particularly limited.
Japanese Patent Laid-Open No. 10-330315

  The acrylic resin composition comprising methyl (meth) acrylate as a main component unit of the present invention has at least a terpene (meth) acrylate as an essential constituent unit as a monomer component, and before being molded into a molded body Say the state. In addition, the introduction method to the acrylic resin composition of terpene type | system | group (meth) acrylic acid ester is not specifically limited. The state before being processed into a molded body is, for example, a polymerization initiator, a chain transfer agent, or the like of a main component unit of a monomer of methyl (meth) acrylate and a monomer of a terpene (meth) acrylate ester Terpene-based (meth) acrylic as a molding material in which various additives are blended with polymers polymerized by polymerization aids, or as a molding material for polymers based on methyl (meth) acrylate Monomer of methyl (meth) acrylate and terpene (meth) acrylic acid ester, which are the main component units in the production of sheets such as cell casting and continuous casting, with oligomers containing acid esters as constituent units (Meth) methyl methacrylate monomer and terpene (meth) as the main component unit in the state of a sheet material obtained by polymerizing the above monomer with a polymerization aid or the like, and before curing to a molded product Shows a state oligomer monomer and / or terpene in acrylic acid ester (meth) acrylate constituent units is blended like.

  When a polymer having methyl (meth) acrylate as a main component constitutes an acrylic resin composition, the polymer is a known suspension polymerization method, bulk polymerization method, solution polymerization method, emulsion polymerization method, photopolymerization method or the like. The polymerization method is not particularly limited.

  Here, as a polymerization method of the polymer or oligomer constituting the acrylic resin composition, a solution polymerization method will be described as an example. For example, as a method of introducing a terpene (meth) acrylate ester, a copolymer of methyl (meth) acrylate as a main unit and a terpene (meth) acrylate ester, a terpene (meth) acrylate ester Examples thereof include a single oligomer and a copolymer oligomer with a monomer that can be copolymerized with a terpene (meth) acrylate. Examples of the copolymerizable monomer include (meth) acrylic acid esters such as methyl (meth) acrylate and ethyl (meth) acrylate. Here, the copolymerization in the present invention indicates not only the state of being incorporated in the polymer chain but also the state of being bonded to the polymer terminal.

  The proportion of the terpene (meth) acrylic acid ester is desirably 0.1 to 50% by mass, and more desirably 1 to 45% by mass. When it is less than 0.1% by mass, the effect of reducing hygroscopicity is small, and when it exceeds 50% by mass, the strength of the acrylic resin is remarkably inferior. However, the amount used can be appropriately changed and used by blending auxiliary materials such as additives and molding agents depending on the type and application of the objective molded body.

  The solution polymerization method includes a step of polymerizing methyl (meth) acrylate or a mixture of methyl (meth) acrylate and terpene (meth) acrylate in an organic solvent using a polymerization initiator. Organic solvents used here include ester solvents such as ethyl acetate and methyl acetate, ketone solvents such as acetone and methyl ethyl ketone, alcoholic solutions such as methanol, ethanol and butanol, and hydrocarbon solutions such as cyclohexane, hexane and heptane. And aromatic solvents such as toluene and xylene. These organic solvents may be used alone or in combination of two or more.

  The polymerization initiator is not particularly limited as long as a desired polymerization rate and degree of polymerization can be obtained. For example, an azo initiator, a peroxide initiator, or the like that is used for normal radical thermal polymerization is used. be able to. Examples of the azo initiator include azobisisobutyronitrile, azobis-4-methoxy-2,4-dimethylvaleronitrile, azobiscyclohexanone-1-carbonitrile, azodibenzoyl, and the like. For example, benzoyl peroxide, lauroyl peroxide, di-t-butylperoxyhexahydroterephthalate, t-butylperoxy-2-ethylhexanoate, 1,1-t-butylperoxy-3,3,5 -Trimethylcyclohexane, t-butylperoxyisopropyl carbonate, etc. are mentioned.

  The polymerization initiator may be used alone or in combination of two or more, and the blending amount is preferably 0.01 to 10% by mass relative to the monomer component of the polymer or oligomer constituting the acrylic resin composition. 0.1 to 8% by mass is particularly preferable. If the blending amount exceeds 10% by mass, the polymer or oligomer tends to be colored by heat, and if it is less than 0.01% by mass, polymerization tends to be difficult. However, the amount used can be appropriately changed and used by blending auxiliary materials such as additives and molding agents depending on the type and application of the objective molded body.

  In the acrylic resin composition containing methyl (meth) acrylate as the main component of the present invention, the weight average molecular weight (Mw) of the polymer containing the methyl (meth) acrylate unit is 10 from the viewpoint of fluidity and mechanical strength. 3,000 to 3,000,000 is preferable, and 30,000 to 1,000,000 is more preferable. Here, the weight average molecular weight (Mw) is measured by gel permeation chromatography and converted to polystyrene.

  An acrylic oligomer may be added to the acrylic resin composition of the present invention, and is not particularly limited. However, (meth) acrylic acid esters such as methyl methacrylate, butyl acrylate, and isobutyl acrylate, and terpene-based (meth) acrylic are used. A homo-oligomer and a copolymer oligomer are mentioned by using acid ester as a monomer component. The acrylic oligomer can be obtained by a known polymerization method such as a suspension polymerization method, a bulk polymerization method, a solution polymerization method, an emulsion polymerization method, or a photopolymerization method, and is not particularly limited. The weight average molecular weight (Mw) of the acrylic oligomer is less than 10,000, preferably 3,000 to 7,000, from the viewpoint of solubility. When the weight average molecular weight (Mw) of the acrylic oligomer is 10,000 or more, it tends to be difficult to be compatible with the composition constituting the acrylic resin composition. The acrylic oligomer is preferably 1 to 50% by weight based on the methyl (meth) acrylate monomer.

  If necessary, the acrylic resin composition may be blended with a low molecular weight modifier to such an extent that the characteristic transparency and weather resistance are not lowered. Although a compounding quantity is not specifically limited, It is preferable to set it as 3-50 mass% with respect to the monomer of methyl (meth) acrylate. Low molecular weight modifiers include (polymerization) rosin, (polymerization) rosin ester, terpene, terpene phenol, coumarone, coumarone indene, styrene resin, xylene resin, phenol resin, petroleum resin And oligomers of the system and the like. These can be used alone or in combination of two or more.

  Furthermore, in addition to the above components, the acrylic resin composition usually contains fillers, pigments, dyes, colorants, diluents, sensitizers, antioxidants, ultraviolet absorbers, ultraviolet stabilizers, light stabilizers, cups Ring agent, anti-yellowing agent, bluing agent, leveling agent, antifoaming agent, thickener, lubricant, polymerization inhibitor, mold release agent, plasticizer, antistatic agent, flame retardant, anti-settling agent, anti-fogging agent Additives such as fiber reinforcement, stone pattern material, and low shrinkage agent may be added as necessary, and these additives can be used alone or in combination of two or more.

  In addition, if necessary, the acrylic resin composition may be added to maleimide derivatives such as N-phenylmaleimide, N-cyclohexylmaleimide, Nt-butylmaleimide, (meth) acrylamide, (meth) acrylonitrile, diacetone acrylamide, dimethylaminoethyl methacrylate. Nitrogen-containing materials such as allyl glycidyl ether, epoxy group-containing monomers such as glycidyl (meth) acrylate, diene monomers such as butadiene, isoprene and chloroprene, styrene-based monomers such as styrene and α-methylstyrene Monomer units composed of monomers such as a body can be used in combination. These monomer units may be used alone or in combination of two or more in a polymer having methyl (meth) acrylate as a unit. The content of these monomer units is preferably 10% by mass or less.

  Although the molding method to the molded body using the acrylic resin composition of the present invention is not particularly limited, transparency and weather resistance can be improved by injection molding, extrusion molding, pressure molding, blow molding, etc. of the acrylic resin composition. A molded article excellent in hygroscopicity can be produced without loss. And such an acrylic resin composition can be used for the material as a use as which these characteristics are requested | required.

  Moreover, when producing a molded object by hardening | curing an acrylic resin composition, it can obtain by a well-known polymerization method, Although it does not specifically limit, thermal polymerization and photopolymerization are mentioned. For example, when performing by radical photopolymerization method, radical photopolymerization initiator can be used.

  The radical photopolymerization initiator is not particularly specified as long as it efficiently absorbs and activates the ultraviolet rays of an industrial UV irradiation apparatus and does not yellow the cured resin. For example, benzoin, benzoin monomethyl ether, benzoin isopropyl Ether, acetoin, benzyl, benzophenone, p-methoxybenzophenone, diethoxyacetophenone, benzyldimethyl ketal, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, methylphenylglyoxylate, 2-hydroxy-2-methyl-1 -Carbonyl compounds such as phenylpropan-1-one, sulfur compounds such as tetramethylthiuram monosulfide, tetramethylthiuram disulfide, 2,4,6-trimethylbenzoyldiphenylphosphine Oxide, 2,4,6-trimethylbenzoylphenylethoxyphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4- Examples thereof include phosphoric acid compounds such as trimethyl-pentylphosphine oxide, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1, camphorquinone, and the like.

  The polymerization initiator may be used alone or in combination of two or more, and the blending amount is 0 with respect to the monomer components of methyl (meth) acrylate and terpene (meth) acrylate constituting the acrylic resin composition. It is preferable to set it as 0.01 to 10 mass%, and it is especially preferable to set it as 0.1 to 8 mass%. If this amount exceeds 10% by mass, the cured product tends to be colored by heat or ultraviolet rays, and if it is less than 0.01% by mass, it tends to be difficult to cure. However, the amount used can be appropriately changed and used by blending auxiliary materials such as additives and molding agents depending on the type and application of the objective molded body.

  Furthermore, a general-purpose radical generation accelerator can be used as necessary. The curing conditions such as curing temperature and nitrogen substitution are not particularly limited as long as the desired polymerization rate and degree of polymerization can be obtained, and ordinary curing conditions are used.

  As a method for curing the acrylic resin composition of the present invention, the acrylic resin composition is cast, potted, or poured into a desired portion, irradiated with active energy rays such as ultraviolet rays and electron beams, and / or heated. It can be done by the method. In order to inhibit curing and prevent coloring, it is desirable to reduce the oxygen concentration in the resin composition in advance by nitrogen bubbling. The curing conditions by thermosetting are not particularly limited as long as the temperature and time at which radical polymerization is finally completed, although it depends on the types, combinations, and addition amounts of the components, and preferably 5 to 60 to 150 ° C. About 10 hours. In order to reduce the internal stress generated by the rapid curing reaction, it is desirable to raise the curing temperature stepwise. In curing by irradiation with ultraviolet rays, a known one such as a high-pressure mercury lamp, a metal halide lamp, an electrodeless discharge lamp represented by fusion can be used. The ultraviolet irradiation can be performed in air or in an inert gas such as nitrogen or argon.

  As a molded body made of the acrylic resin composition of the present invention, a disk material such as a video disk, an audio disk, and a write-once disk for computers, a lens material such as a camera, a video camera, a projection television, and an optical pickup, an optical fiber, Various optical transmission materials such as optical connectors, light guide plate, diffuser plate, optical disk, PTTV lenticular lens, PITV full-lens lens, pickup lens, camera lens, video lens, glasses, display front plate, prism, optical fiber, etc. In addition to parts, etc., transparent substrates, lenses, adhesives, sealing materials, optical waveguides, light emitting diodes (LEDs), phototransistors, photodiodes, optical members for use in optical semiconductor elements such as solid-state imaging devices, lighting covers, lamps Shade, chandelier Lighting products, showcases, partition plates, display products such as store displays, vehicle lamp covers, vehicle side visors, meter covers, windshields and other transportation equipment parts, stereo covers, nameplates and other electronic equipment parts, and more Special products include artificial marble and molded parts such as dentures or molded parts.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited to these. In the examples and comparative examples, parts and% are based on weight unless otherwise specified.

<Analysis method>
The following apparatus was used for the analysis in an Example.
1. Purity: determined by a gas chromatography mass spectrometer (GC-MS). Apparatus: Hewlett Packard, HP6890 GC System, column: HP-5MS (Crosslinked 5% Ph Me Siloxane) diameter 0.25 mm × 30 m, ionization mode: EI
2. Molecular weight: The weight average molecular weight (Mw) was determined by gel permeation chromatography (GPC). Apparatus: Waters, model 510, column: Waters, Styragel (HR5 + HR4) × 2, solvent: tetrahydrofuran, standard material: polystyrene

Synthesis example 1
(Synthesis of terpene methacrylate (R1 = methyl group) represented by formula (1))
After charging 110 parts of phenol and 20 parts of strongly acidic cation exchange resin into a polymerization apparatus equipped with a thermometer, a stirring device, a dropping funnel and a condenser, Kanfen (Yasuhara Chemical Co., Ltd.) was maintained at a temperature of 80 ° C. (Product, purity 95%) was added dropwise 135 parts, followed by post-reaction with stirring. Next, the strongly acidic cation exchange resin was removed from the reaction solution, 300 parts of toluene was added and dissolved, washed with distilled water, and then distilled under reduced pressure to obtain a fraction having a boiling point of 138 ° C. to 148 ° C./5 mmHg. The above fraction, 200 parts of 2-propanol and 1 part of a powdery 5% ruthenium-supported alumina catalyst were charged into an autoclave, and hydrogen gas was introduced. The mixture was heated to 150 ° C. with stirring and reacted at a hydrogen pressure of 40 kg / cm 2. Thereafter, the mixture was cooled to room temperature, 300 parts of ethanol was added, and the catalyst was filtered off. Concentration under reduced pressure using an evaporator gave 17.6 parts of an alicyclic hydroxy compound represented by the formula (12) having a purity by gas chromatography of 95%.
Next, 12 parts of the alicyclic hydroxy compound represented by the formula (12) obtained above and 50 parts of toluene, 5 parts of methacrylic acid, 0.1 part of concentrated sulfuric acid, hydroquinone were installed in a reactor equipped with an oil / water separator equipped with a reflux device. 0.05 part was charged and reacted at 110 ° C. with heating and stirring. Next, the reaction oil was washed with water and distilled under reduced pressure to distill off toluene and unreacted substances to obtain a slightly yellow liquid as a residue. Next, purification was performed by column chromatography to obtain 10 parts of a terpene methacrylic acid derivative (R1 = methyl group) represented by the formula (1).

Synthesis example 2
(Synthesis of terpene methacrylate (R2 = methyl group) represented by formula (2))
The same operation as in Synthesis Example 1 was carried out except that camphene was changed to paramentene 1, to obtain 19 parts of an alicyclic hydroxy compound represented by the formula (13) having a purity of 92% according to gas chromatography.
Furthermore, the same operation as in Synthesis Example 1 was performed except that the alicyclic hydroxy compound represented by formula (12) was changed to the alicyclic hydroxy compound represented by formula (13) obtained above, and represented by formula (2) 9 parts of terpene methacrylate (R2 = methyl group) were obtained.

Example of preparation of single oligomer (Synthesis of single oligomer of terpene methacrylate (R2 = methyl group) represented by formula (2))
In a polymerization apparatus equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen introduction tube, 100 parts of a terpene methacrylate (R2 = methyl group) represented by the formula (2), thioglycolic acid (mercaptoacetic acid, Sakai Chemical Industry ( 3 parts) and 0.05 part of di-tert-hexyl peroxide were charged, and nitrogen-sealed for 1 hour with stirring at room temperature. Next, this mixture was stirred while gently blowing nitrogen gas, and the temperature was raised to 70 ° C. to initiate the polymerization reaction. The polymerization reaction in the first stage was carried out for about 2 hours so that the temperature inside the apparatus, which was raised by the generated reaction heat, was maintained at 70 to 80 ° C. Here, 0.05 part of di-tert-hexyl peroxide was added, and after the temperature rise in the reaction system caused by self-generated heat became moderate, the temperature in the reaction system was gradually raised to 170 ° C. The terpene methacrylate (R2 = methyl group) represented by the formula (2) in which the second stage polymerization reaction is performed for 4 to 6 hours, the conversion is about 95%, and the weight average molecular weight (Mw) is 4,000. ) Single oligomer (A) was obtained.

Example 1
Methyl methacrylate: 100 parts by weight of a terpene methacrylate (R1 = methyl group) represented by the formula (1) = 80: 20 was prepared, and α, α′-azobisisobutyronitrile 0 was used as a polymerization initiator. .2 parts, 150 parts of toluene as a solvent were charged into a polymerization apparatus equipped with a thermometer, a stirrer, an inert gas introduction tube, and a reflux condenser. The reaction was carried out by stirring while raising the temperature in the polymerization apparatus to 70 ° C. under a nitrogen stream. Further, 1,500 parts of hexane was added and gradually cooled to room temperature. The precipitated crystals were filtered off and the solvent was removed to obtain 55 parts of crystals having a weight average molecular weight (Mw) of 220,000.

Example 2
The same operation as Example 1 was carried out except that the terpene methacrylate (R2 = methyl group) represented by the formula (2) was blended instead of the terpene methacrylate (R1 = methyl group) represented by the formula (1). And 50 parts of crystals with a weight average molecular weight (Mw) of 230,000 were obtained.

Example 3
Prepare 100 parts of methyl methacrylate, 0.06 part of α, α'-azobisisobutyronitrile as a polymerization initiator, 150 parts of ethyl acetate as solvent, thermometer, stirrer, inert gas introduction tube, reflux cooling The polymerization apparatus equipped with a vessel was charged. Stirring was performed while raising the temperature in the polymerization apparatus to 55 ° C. in a nitrogen stream, and the reaction was performed. Further, 1500 parts of hexane was added and gradually cooled to room temperature. The precipitated crystals were separated by filtration and the solvent was removed. As a result, 20.2 g of resin (B) crystals having a weight average molecular weight (Mw) of 200,000 were obtained. Obtained.
Furthermore, using the resin (B), 20 parts of a single oligomer (A) of a terpene methacrylate (R2 = methyl group) represented by the formula (2) was added to 100 parts of the resin (B).

Comparative Example 1
Resin (B) was used.

Comparative Example 2
The same operation as Example 1 was carried out except that isobornyl methacrylate (trade name “IBX”, manufactured by Osaka Organic Chemical Co., Ltd.) was blended in place of the terpene methacrylate (R1 = methyl group) represented by the formula (1). And 50 parts of crystals with a weight average molecular weight (Mw) of 230,000 were obtained.

  Examples 1 to 3 and Comparative Examples 1 and 2 were dissolved in tetrahydrofuran, respectively, and the thickness after drying on a polyethylene terephthalate (PET) film (manufactured by Toray Industries, Inc .: thickness 38 μm) as a substrate was 20 to 30 μm. Then, the coating was dried at 100 ° C. for 1 minute. Thereafter, the sample was prepared by drying at room temperature for 24 hours.

<Evaluation method>
The evaluation method is as follows.
1. Hygroscopicity: Measured according to JIS K 7209 "Plastics-Determination of water absorption". The sample adjusted to 5 cm × 5 cm was placed in a 120 ° C. dryer overnight and sufficiently dried, and then the weight (W1) was measured. Next, this sample was immersed in distilled water at 23 ° C. and left for 192 hours. After taking out from the water, the cloth was wiped off with water and allowed to stand for 2 minutes. Then, the weight (W2) was measured, and the water absorption was determined by the following formula.
Water absorption (%) = [(W2−W1) / W1] × 100
2. Transparency: The haze of the sample was measured with COH-300A manufactured by Nippon Denshoku Industries Co., Ltd.
3. Weather resistance: Put a sample in Table Sun XT750 manufactured by Suga Test Instruments Co., Ltd., and illuminate 48,0001x, irradiation 100 hours, temperature 50 ° C., then yellowness ( ΔYI value) was measured.

Example 4
80 parts of methyl methacrylate, terpene methacrylate (R1 = methyl group) represented by formula (1), and 1-hydroxycyclohexyl phenyl ketone (trade name “Irgacure 184”, Ciba Specialty Chemicals) as a photo radical polymerization initiator 1 part by weight was mixed at room temperature to prepare a resin composition. This resin composition was poured into a mold in which a 1 mm thick silicone spacer was sandwiched between glass plates, and radical polymerization was performed using an ultrahigh pressure mercury lamp at an illuminance of 11.6 mW / cm 2 and an integrated exposure of 3000 mJ / cm 2.

Example 5
The same operation as Example 4 was carried out except that the terpene methacrylate (R2 = methyl group) represented by the formula (2) was blended instead of the terpene methacrylate (R1 = methyl group) represented by the formula (1). went.

Example 6
50 parts of methyl methacrylate, 50 parts of a terpene methacrylate ester (R2 = methyl group) single oligomer (A) represented by the formula (2), α, α′-azobisisobutyronitrile as a polymerization initiator; 4 parts were mixed at room temperature to prepare a resin composition. This resin composition is poured into a mold in which a 1 mm thick silicone spacer is sandwiched between glass plates and heated in an oven at 60 ° C. for 5 hours and at 80 ° C. for 2 hours to obtain a 1 mm thick cured product. It was.

Comparative Example 3
100 parts of methyl methacrylate and 1 part by weight of 1-hydroxycyclohexyl phenyl ketone (trade name “Irgacure 184”, manufactured by Ciba Specialty Chemicals Co., Ltd.) as a radical photopolymerization initiator are mixed at room temperature to obtain a resin composition Adjusted. This resin composition was poured into a mold in which a 1 mm thick silicone spacer was sandwiched between glass plates, and radical polymerization was performed using an ultrahigh pressure mercury lamp at an illuminance of 11.6 mW / cm 2 and an integrated exposure of 3000 mJ / cm 2.

Comparative Example 4
The same operation as in Example 4 except that isobornyl methacrylate (trade name “IBX”, manufactured by Osaka Organic Chemical Co., Ltd.) was blended in place of the terpene methacrylate (R1 = methyl group) represented by the formula (1). Went.

  About the hardened | cured material obtained in Examples 4-6 and Comparative Examples 3 and 4, hardening shrinkage property was measured by the method shown below.

<Evaluation method>
1. Curing shrinkage: The curing shrinkage was calculated from the specific gravity (a) of the resin composition and the specific gravity (b) of the cured product using the following formula.
Curing shrinkage (%) = [(ba) / b] × 100

Industrial applicability

  An acrylic resin composition having at least a terpene (meth) acrylic acid ester of formula (1) and / or formula (2) as an essential constituent unit as a monomer component according to the present invention is used for video discs, audio discs and computers. Disc materials such as write-once discs, lens materials for cameras, video cameras, projection televisions, optical pickups, various optical transmission materials such as optical fibers and optical connectors, light guide plates, diffusion plates, optical discs, lenticular lenses for PTTV , PITV full-lens lenses, pickup lenses, camera lenses, video lenses, glasses, display front plates, prisms, optical fibers and other optical components, as well as transparent substrates, lenses, adhesives, sealing materials, optical waveguides, light emission Diode (LED), phototransistor, photo Optical members for optical semiconductor elements such as diodes and solid-state image sensors, lighting covers, lamp shades, lighting products such as chandeliers, display products such as showcases, partition plates, store displays, vehicle lamp covers, vehicle side visors, meters It can also be used for parts for transportation equipment such as covers and windshields, electronic equipment parts such as stereo covers and nameplates, and also for artificial marble and dentures as special products.

Claims (4)

  A terpene derived from an esterification reaction of an alicyclic hydroxy compound having 12 to 26 carbon atoms having a terpene skeleton and a (meth) acrylic acid compound in an acrylic resin composition containing methyl (meth) acrylate as a main unit. An acrylic resin composition comprising a system (meth) acrylic acid ester as an essential constituent unit.   2. The acrylic resin composition according to claim 1, wherein, in the terpene-based (meth) acrylic acid ester, the difference in the contribution rate of Hansen solubility parameter starting from butyl acrylate is 11.0 or more. The acrylic resin composition according to claim 1 or 2, wherein the terpene (meth) acrylic ester is represented by the following formula (1) and / or formula (2).

In the above formula, R1 represents a hydrogen atom or a methyl group.

In the above formula, R2 represents a hydrogen atom or a methyl group.   The molded object which consists of an acrylic resin composition in any one of Claims 1-3.