WO2020195938A1 - In-mold coating composition - Google Patents

In-mold coating composition Download PDF

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Publication number
WO2020195938A1
WO2020195938A1 PCT/JP2020/011059 JP2020011059W WO2020195938A1 WO 2020195938 A1 WO2020195938 A1 WO 2020195938A1 JP 2020011059 W JP2020011059 W JP 2020011059W WO 2020195938 A1 WO2020195938 A1 WO 2020195938A1
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WIPO (PCT)
Prior art keywords
ethylenically unsaturated
unsaturated monomer
acrylate
mold
meth
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PCT/JP2020/011059
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French (fr)
Japanese (ja)
Inventor
山中　英幸
前田　浩志
小林　稔幸
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大日本塗料株式会社
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Application filed by 大日本塗料株式会社 filed Critical 大日本塗料株式会社
Priority to JP2020549734A priority Critical patent/JP6800392B1/en
Publication of WO2020195938A1 publication Critical patent/WO2020195938A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts

Definitions

  • the present invention relates to a composition for inner coating of a mold, and more particularly to a composition for inner coating of a mold used for a fiber reinforced plastic.
  • Fiber reinforced plastic moldings such as glass fiber, carbon fiber, organic fiber, mineral fiber, etc., which have a matrix of thermosetting resin or thermoplastic resin such as sheet molding compound (SMC), bulk molding compound (BMC), stampable sheet, etc. Since the molded product obtained from is excellent in mechanical strength, moldability, etc., and is lightweight, it is widely used in the fields of electrical equipment such as parabona antennas, automobile outer panels, housing equipment parts, etc. as a material to replace metal. It's being used.
  • SMC sheet molding compound
  • BMC bulk molding compound
  • these molded products have surface defects such as pinholes, burrows, microcracks, and fiber patterns, have low gloss, have poor appearance quality, and have weather resistance, water resistance, chemical resistance, and the like. There was a problem that it was bad and the hardness was low.
  • An object of the present invention is to provide a mold inner coating composition for fiber reinforced plastics having excellent smoothness, adhesiveness, water resistance and weather resistance.
  • the present inventors have achieved the object by the following.
  • the composition contains the urethane (meth) acrylate (A), the monofunctional ethylenically unsaturated monomer (B) having an alicyclic structure, and the monofunctional ethylenically unsaturated monomer (C).
  • the fiber-reinforced plastic molded product according to 1 above which contains 40 to 85% by mass, 10 to 40% by mass, and 5 to 20% by mass, respectively, with respect to the total amount of the ethylenically unsaturated monomer. Mold inner coating composition. 3. 3.
  • the fiber according to 1 or 2 above, wherein the glass transition temperature (Tg) of the polymer obtained from the monofunctional ethylenically unsaturated monomer (B) having an alicyclic structure is 80 to 250 ° C.
  • a mold inner coating composition for a fiber reinforced plastic having excellent smoothness, adhesiveness, water resistance and weather resistance.
  • (meth) acrylate means both acrylate and methacrylate.
  • the mold inner coating composition for the fiber-reinforced plastic molded product of the present invention comprises at least a urethane (meth) acrylate (A), a monofunctional ethylenically unsaturated monomer (B) having an alicyclic structure, and the above (A). ) And (B), the urethane (meth) acrylate containing at least one monofunctional ethylenically unsaturated monomer (C), a mold release agent (D) and an initiator (E).
  • At least one of (A) is characterized in that the weight average molecular weight is 600 or more and 7,000 or less, and the number of functional groups is 2 or more and 4 or less.
  • the weight average molecular weight of the urethane (meth) acrylate is 600 or more and 7,000 or less, and the number of functional groups is 2 or more and 4 or less, the smoothness is excellent.
  • the urethane (meth) acrylate (A) of the present invention is a compound in which a (meth) acrylate group is added to a reaction product of a diol and an isocyanate, and in particular, a reaction product of an aliphatic diol and an aliphatic isocyanate containing no aromatic ring can be used. It is preferably an aliphatic (meth) acrylate to which a (meth) acrylate group is added.
  • the urethane (meth) acrylate (A) of the present invention can generally be obtained by collectively mixing and reacting a diisocyanate compound, a diol compound and a hydroxyl group-containing (meth) acrylate.
  • a diol compound and a diisocyanate compound are reacted to form a urethane isocyanate intermediate containing one or more isocyanate groups per molecule, and then this intermediate and a hydroxyl group-containing (meth) acrylate are formed.
  • a method of reacting with, a diisocyanate compound is reacted with a hydroxyl group-containing (meth) acrylate to form a urethane (meth) acrylate intermediate containing one or more isocyanate groups per molecule, and then with this intermediate.
  • Examples thereof include a method of reacting with a diol compound.
  • diisocyanate compound of the present invention various known diisocyanate compounds can be used, for example, 1,2-diisocyanatoethane, 1,2-diisocyanatopropane, 1,3-diisocyanatopropane, hexamethylene diisocyanate.
  • diisocyanates may be used alone or as a mixture thereof. Of these, those having a ring structure in the structure are preferable, and those having 3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate and 1,3-bis (3,5,5-trimethylcyclohexylisocyanate) are particularly preferable. Isocyanatomethyl) cyclohexane, or bis (4-isocyanatocyclohexyl) methane.
  • Examples of the diol compound of the present invention include alkyldiols.
  • Examples of the alkyl diol include ethylene glycol, 1,3-propanediol, propylene glycol, 2,3-butanediol, 1,4-butanediol, 2-ethylbutane-1,4-diol, and 1,5-pentadiol.
  • Decane 2,2-bis (4-hydroxycyclohexyl) propane, 2,2-diethylpropane-1,3-diol, 2,2-dimethylpropane-1,3-diol, 3-methylpentane-1,4 -Diol, 2,2-diethylbutane-1,3-diol, 4,5-nonanediol, 2-butene-1,4-diol
  • Examples of the hydroxyl group-containing (meth) acrylate used in the production of the aliphatic urethane (meth) acrylate of the present invention include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. ) Acrylate, 1,4-cyclohexanedimethanol monoacrylate and the like.
  • the number of (meth) acrylates at the end of the aliphatic urethane (meth) acrylate can be selected from 1 to 6, but is preferably 2 to 4.
  • the urethane (meth) acrylate of the present invention preferably has at least one type having a weight average molecular weight of 600 to 7000.
  • the weight average molecular weight can be measured by size exclusion chromatography.
  • polystyrene is used as a standard substance.
  • the aliphatic urethane (meth) acrylate of the present invention can be contained in an amount of 10 to 95% by mass and 40 to 85% by mass with respect to the total amount of the ethylenically unsaturated monomer contained in the coating composition of the present invention. It is preferable to let it. Two or more types can be mixed and used.
  • Examples of the monofunctional ethylenically unsaturated monomer (B) having an alicyclic structure of the present invention include olefins such as alicyclic (meth) acrylate, cyclohexene, vinylcyclohexane, cyclopentene, 1-methylcyclohexene, and cycloheptene.
  • olefins such as alicyclic (meth) acrylate, cyclohexene, vinylcyclohexane, cyclopentene, 1-methylcyclohexene, and cycloheptene.
  • an alicyclic (meth) acrylate is preferable, and an alicyclic (meth) acrylate having a glass transition temperature Tg of a polymer obtained from a monomer of 80 to 250 ° C. is particularly preferable.
  • the alicyclic (meth) acrylate having a Tg of 80 ° C. or higher of the present invention can be used as a mixture of two or more.
  • the monofunctional ethylenically unsaturated monomer (B) having an alicyclic structure of the present invention is contained in an amount of 5 to 50% by mass based on the total amount of the ethylenically unsaturated monomer contained in the coating composition of the present invention. It can be contained, and it is preferable to contain 10 to 40% by mass. Two or more types can be mixed and used.
  • the monofunctional ethylenically unsaturated monomer (C) copolymerizable with (A) and (B) of the present invention is copolymerized with (A) and (B) and is different from (B). If there is no particular limitation, an aromatic monomer having a melting point (mp) of 0 ° C. or lower is preferable.
  • styrene (-30 ° C), ⁇ -methylstyrene (-23 ° C), ⁇ -methylstyrene (-27 ° C), p-methylstyrene (-77 ° C), 4-methylstyrene (-34 ° C), 3-ethylstyrene. (-101 ° C.), 2-ethylstyrene (-76 ° C.), hydroxyethyl methacrylate (-12 ° C.), hydroxyethyl acrylate (-60 ° C.), hydroxypropyl methacrylate (-58 ° C.) and the like.
  • a hydroxy group-containing monomer is preferable, and the hydroxyl group-containing (meth) acrylate used in the production of the aliphatic urethane (meth) acrylate of the present invention can be used as it is.
  • the hydroxyalkyl (meth) acrylate of the present invention can also be used by mixing two or more kinds.
  • the (C) of the present invention can be contained in an amount of 1 to 30% by mass, preferably 5 to 20% by mass, based on the total amount of the ethylenically unsaturated monomer contained in the coating composition of the present invention. .. Two or more types can be mixed and used.
  • the ethylenically unsaturated monomer contained in the composition is contained in an amount of 5 to 60% by mass based on the total amount of the ethylenically unsaturated monomer because the adhesion to the substrate is excellent.
  • the calculation method of the SP value in the present invention is shown below.
  • the SP value is a numerical value peculiar to the resin composition and serves as a guide for determining compatibility.
  • SP by the vapor pressure method proposed by Hoy is used.
  • the molecular attraction constants obtained using the values, the literature K.L. Hoy, J. Paint Technology, 42, [541], 76 (1970) (K. L. Hoy, J. Paint Technology, 42, It means a value calculated according to the method described in [541], 76 (1970)).
  • the mold release agent (D) used in the present invention is added so that the cured film can be smoothly released from the mold, and the types thereof are stearates such as zinc, aluminum, magnesium, and calcium. , Lecithin, alkyl phosphate, etc. are typical examples, but the present invention is not limited to these.
  • the release agent (D) is preferably blended in an amount of 0.05 to 4% by mass in the coating composition.
  • the polymerization initiator (E) used in the present invention is blended to generate free radicals, polymerize the monomer component, and cure the coating film.
  • polymerization initiators tertiary butyl perbenzoate, tertiary butyl peroctate, methyl ethyl ketone peroxide, tertiary benzyl perbenzoate, dicumyl peroxide, cumyl hydroperoxide, diacetyl peroxide, caprylyl peroxide, tertiary Butyl hydroperoxide and the like are typical examples, but the present invention is not limited thereto.
  • the polymerization initiator (E) is preferably blended in an amount of 0.1 to 5% by mass based on the monomer component.
  • the coating composition of the present invention can further contain various additives such as pigments, curing accelerators, dispersants, sedimentation inhibitors, flow aids, polymerization inhibitors, and ultraviolet absorbers, if necessary.
  • the pigment does not necessarily have to be blended, but it colors the molded product to give it an aesthetic appearance, disperses the shrinkage stress associated with the curing of the film, improves the adhesion to the molded product, and on the surface of the molded product. It can be contained for the purpose of filling existing burrows and the like, smoothing minute irregularities on the surface, and further providing functions such as conductivity.
  • coloring pigments and extender pigments that have been conventionally used for plastics and paints can be used without particular limitation.
  • coloring pigments include titanium oxide for whites, benzidine yellow, titanium yellow, and Hansa yellow for yellows; molybdate orange, chrome yellow, and benzidine oranges for oranges; quinacridone and maroon for reds; carbon for blacks.
  • Typical examples include powder pigments such as black and iron oxide, and flaky pigments such as flaky aluminum, copper, stainless steel, mica, graphite, and titanium nitride.
  • the pigment can be contained in an arbitrary amount in the coating composition depending on the above-mentioned purpose, but usually up to 40% by mass in the case of a coloring pigment and up to 50% by mass in the case of an extender pigment, both of which are suitable. When used in combination, it is preferably contained up to 65% by mass.
  • a heat-curable resin such as unsaturated polyester resin-based, epoxy acrylate resin-based, phenol resin-based, or epoxy resin-based or thermoplastic resin such as polyolefin resin-based, polystyrene resin-based, or polycarbonate resin-based is used as a matrix.
  • a typical example is a fiber-reinforced plastic molded product.
  • the fiber used in the fiber-reinforced plastic molded product examples include glass fiber, carbon fiber, organic fiber, and mineral fiber.
  • the coating composition of the present invention is also applied to a plastic molded product reinforced with carbon fiber. Can be preferably applied.
  • a conventional method of molding in a mold can be used without particular limitation, but there is preferably a method described in JP-A-5-70712. That is, a cavity having the shape of the target molded product by fitting one mold into the other mold (hereinafter, for convenience, the former is referred to as “lower mold” and the latter is referred to as “upper mold”).
  • a carbon fiber reinforced plastic molded product is placed in a mold that forms a space, and is fitted and molded in the mold.
  • the molded product when it uses a thermosetting resin as a matrix, it is heated and pressurized in the mold to allow the molded product to flow and undergo a thermosetting reaction to form the desired shape.
  • the molding heating temperature is arbitrarily determined depending on the molding time, the type of the molded product, etc., but is usually preferably 130 to 200 ° C., and the mold is set to the above temperature in advance before inserting the molded product to obtain a desired cured film. It is desirable to keep the temperature at that temperature until
  • the molding pressure is arbitrarily determined depending on the heating temperature, the type of molded product, etc., but is usually preferably 5 to 20 MPa.
  • the molding time may be until the molded product completely completes the thermosetting reaction, but when the coating composition described later is injected, the molded product may be cured to a strength that does not impair the shape of the molded product, and is usually 40 to 200. About seconds is preferable.
  • the molded product uses a thermoplastic resin as a matrix
  • the material previously heated and softened by a heating oven or the like is pressed in a mold to allow the molded product to flow and to be molded into a desired shape, and the coating composition described later.
  • the product is injected, it is cured to a strength that does not damage the shape of the molded product.
  • the upper mold is separated from the surface of the molded product, which is larger than the desired cured film thickness to be described later, but is insufficient to release the fitting of the mold.
  • An amount sufficient to obtain a desired film thickness preferably 10 to 1000 ⁇ m, after giving a gap, maintaining the molding pressure with the mold fitted, or reducing the pressure.
  • the coating composition of is injected (injection injection) between the upper mold and the surface of the molded product.
  • the coating composition uniformly covers the surface of the molded product and permeates the molded product while maintaining the heating temperature at about 1 to 14 MPa (re).
  • the pressure is usually maintained for about 30 to 120 seconds until a cured film is formed.
  • the coating composition is uniform while maintaining the mold temperature at a temperature at which the molded product does not resoften and the coating composition cures, for example, 60 to 160 ° C.
  • the surface of the molded product is covered and (re) pressurized to about 1 to 14 MPa so as to penetrate, and usually maintained for about 30 to 150 seconds until a cured film is formed.
  • a curing accelerator such as cobalt naphthenate or amine may be used in combination.
  • the mold is opened and the molded product is taken out to obtain a molded product having a protective film.
  • Adhesion between the base material and the coating film ⁇ The obtained mold inner coating molded product was subjected to an adhesion test according to JIS K 5600-5-6: 1999 (adhesion (cross-cut method)). The interval between cuts was 2 mm, and the appearance of the coating film by the cellophane tape peeling test on 100 grids was visually evaluated. The adhesiveness of the coating film was evaluated on a scale of 0 to 5 below based on the classification of the test results described in JIS K 5600-5-6. The evaluation was performed at 5 locations each, and the results were displayed as average values. -Category 0: The edges of the cut are completely smooth, and there is no peeling in the eyes of any grid.
  • -Category 1 The residual rate of the laminated coating film is 95 to 99%.
  • -Category 2 The residual rate of the laminated coating film is 85% or more and less than 95%.
  • -Category 3 The residual rate of the laminated coating film is 65% or more and less than 85%.
  • -Category 4 The residual rate of the laminated coating film is 0% or more and less than 65%.
  • -Category 5 Degree of peeling that cannot be classified even in Category 4.
  • Accelerated weather resistance ⁇ The obtained mold inner coating molded product was subjected to an accelerated weather resistance test by a weather meter Ci4000 (manufactured by Atlas) according to the xenon lamp method described in JIS K 5600-7-7: 2008. This was carried out until the radiation exposure amount reached 500 MJ, and the appearance of the coating film was visually evaluated.
  • the evaluation criteria are as follows. Pass: No blistering or gloss loss occurs. Fail: Blisters or gloss loss occur.
  • Moisture resistance of coated part ⁇ The obtained mold inner coating molded product was subjected to a moisture resistance test (test conditions: 80 ⁇ 1 ° C., relative humidity 95% or more, test time 48 hours) according to JIS K 5600-7-2: 1999. In the evaluation, wrinkles, swelling, cracks, rust, peeling, etc. were not observed in the coating film by observation immediately after the test and after standing in the room for 2 hours, and the appearance of the coating film after standing for 2 hours was visually evaluated. did. Passed: No cloudiness, whitening or discoloration. Fail: Cloudy, whitening, discoloration, etc. are observed.
  • the mold inner coating composition of the present invention is excellent in adhesion, weather resistance, moisture resistance and smoothness.

Abstract

The purpose of the present invention is to provide an in-mold coating composition for fiber reinforced plastic with excellent smoothness, adhesion, water resistance and weatherability.　The present invention achieves this purpose with an in-mold coating composition for a fiber reinforced plastic molded body, characterized by containing at least urethane (meth)acrylate (A) and a monofunctional ethylenically unsaturated monomer (B) having an alicyclic structure, at least one type of monofunctional ethylenically unsaturated monomer (C) that is co-polymerizable with (A) and (B), a release agent (D) and an initiator (E), wherein at least one type of the urethane (meth)acrylate (A) has a 600-7000 weight average molecular weight and 2-4 functional groups.

Description

型内被覆用組成物Mold inner coating composition
　本発明は、型内被覆用組成物に関し、詳しくは繊維強化プラスチックに使用される型内被覆用組成物に関する。 The present invention relates to a composition for inner coating of a mold, and more particularly to a composition for inner coating of a mold used for a fiber reinforced plastic.
　シートモールディングコンパウンド（ＳＭＣ）、バルクモールディングコンパウンド（ＢＭＣ）、スタンパブルシート等の熱硬化性樹脂もしくは熱可塑性樹脂をマトリックスとする、ガラス繊維、炭素繊維、有機繊維、ミネラル繊維等の繊維強化プラスチック成形物から得られる成形物は、機械的強度、成形性などに優れ、かつ軽量であることから、金属に代る材料として、パラボナアンテナ等の電気機器、自動車外板、住宅設備部品などの分野に広く利用されている。   Fiber reinforced plastic moldings such as glass fiber, carbon fiber, organic fiber, mineral fiber, etc., which have a matrix of thermosetting resin or thermoplastic resin such as sheet molding compound (SMC), bulk molding compound (BMC), stampable sheet, etc. Since the molded product obtained from is excellent in mechanical strength, moldability, etc., and is lightweight, it is widely used in the fields of electrical equipment such as parabona antennas, automobile outer panels, housing equipment parts, etc. as a material to replace metal. It's being used.
　しかしながらこれらの成形物は、ピンホール、巣穴、微小クラック、ファイバーパターンなどの表面欠陥を有しており、また光沢も低く、外観品質が悪く、さらに耐候性、耐水性、耐薬品性等が悪く、硬度も低いといった問題点があった。 However, these molded products have surface defects such as pinholes, burrows, microcracks, and fiber patterns, have low gloss, have poor appearance quality, and have weather resistance, water resistance, chemical resistance, and the like. There was a problem that it was bad and the hardness was low.
　従って、これらの成形物は、通常塗料を塗装し、表面に保護被膜を形成させているが、前述の通り成形物は多くの表面欠陥を有しているため、スプレー等の通常の塗装手段にて塗装しても、平滑性等の外観に優れた被膜が形成しにくく、また付着性も低く、さらに塗装作業性等も悪いといった問題点があった。そのためこれら問題点を解決する方法として、型内被膜方法およびそのための塗料組成物が提案されている（特許文献１、２）。 Therefore, these molded products are usually coated with a paint to form a protective film on the surface, but as described above, the molded products have many surface defects, so that they can be used for ordinary coating means such as spraying. There are problems that it is difficult to form a film having excellent appearance such as smoothness, the adhesiveness is low, and the painting workability is also poor. Therefore, as a method for solving these problems, a mold inner coating method and a coating composition for that purpose have been proposed (Patent Documents 1 and 2).
特開平５－７０７１２号公報Japanese Unexamined Patent Publication No. 5-70712 特開平１０－２０４１３５号公報Japanese Unexamined Patent Publication No. 10-204135
　しかしながら、上記の塗料組成物であっても平滑性、付着性、耐水性および耐候性は十分ではなく、繊維強化プラスチック、特に炭素繊維強化プラスチックでそれが顕著であった。 However, even with the above coating composition, smoothness, adhesiveness, water resistance and weather resistance were not sufficient, and it was remarkable in fiber reinforced plastics, especially carbon fiber reinforced plastics.
　本発明は、平滑性、付着性、耐水性および耐候性に優れた繊維強化プラスチック用の型内被覆組成物を提供することを目的とする。 An object of the present invention is to provide a mold inner coating composition for fiber reinforced plastics having excellent smoothness, adhesiveness, water resistance and weather resistance.
　本発明者らは、下記によって目的を達成した。 The present inventors have achieved the object by the following.
１．　少なくとも、ウレタン（メタ）アクリレート（Ａ）と脂環式構造を有する単官能エチレン性不飽和単量体（Ｂ）、該（Ａ）および（Ｂ）と共重合可能である少なくとも1種の単官能エチレン性不飽和単量体（Ｃ）、離型剤（Ｄ）ならびに開始剤（Ｅ）とを含み、
該ウレタン（メタ）アクリレート（Ａ）の少なくとも１種は、重量平均分子量が６００以上７０００以下であり、さらに、官能基数が２以上４以下であることを特徴とする繊維強化プラスチック成形物用の型内被覆組成物。
２．前記ウレタン（メタ）アクリレート（Ａ）、前記脂環式構造を有する単官能エチレン性不飽和単量体（Ｂ）および前記単官能エチレン性不飽和単量体（Ｃ）が、前記組成物に含まれるエチレン性不飽和単量体の総量に対してそれぞれ４０～８５質量％、１０～４０質量％および５～２０質量％含有されることを特徴とする前記１に記載の繊維強化プラスチック成形物用の型内被覆組成物。
３．前記脂環式構造を有する単官能エチレン性不飽和単量体（Ｂ）から得られるポリマーのガラス転移温度（Ｔｇ）が８０～２５０℃であることを特徴とする前記１又は２に記載の繊維強化プラスチック成形物用の型内被覆組成物。
４．前記脂環式構造を有する単官能エチレン性不飽和単量体（Ｂ）と単官能エチレン性不飽和単量体（Ｃ）のうち、溶解度パラメーターＳＰ値が９．５以下のものが、前記組成物に含まれるエチレン性不飽和単量体の総量に対して５～６０質量％含まれていることを特徴とする前記１～３のいずれかに記載の繊維強化プラスチック成形物用の型内被覆組成物。 1. 1. At least a monofunctional ethylenically unsaturated monomer (B) having an alicyclic structure with a urethane (meth) acrylate (A), and at least one monofunctional copolymerizable with the (A) and (B). It contains an ethylenically unsaturated monomer (C), a mold release agent (D) and an initiator (E).
At least one of the urethane (meth) acrylates (A) has a weight average molecular weight of 600 or more and 7,000 or less, and further has a functional group number of 2 or more and 4 or less, which is a mold for a fiber reinforced plastic molded product. Inner coating composition.
2. 2. The composition contains the urethane (meth) acrylate (A), the monofunctional ethylenically unsaturated monomer (B) having an alicyclic structure, and the monofunctional ethylenically unsaturated monomer (C). The fiber-reinforced plastic molded product according to 1 above, which contains 40 to 85% by mass, 10 to 40% by mass, and 5 to 20% by mass, respectively, with respect to the total amount of the ethylenically unsaturated monomer. Mold inner coating composition.
3. 3. The fiber according to 1 or 2 above, wherein the glass transition temperature (Tg) of the polymer obtained from the monofunctional ethylenically unsaturated monomer (B) having an alicyclic structure is 80 to 250 ° C. In-mold coating composition for reinforced plastic moldings.
4. Of the monofunctional ethylenically unsaturated monomer (B) and the monofunctional ethylenically unsaturated monomer (C) having an alicyclic structure, those having a solubility parameter SP value of 9.5 or less have the composition. The inner coating for a fiber-reinforced plastic molded product according to any one of 1 to 3 above, wherein the ethylenically unsaturated monomer is contained in an amount of 5 to 60% by mass based on the total amount of the ethylenically unsaturated monomer. Composition.
　本発明によれば、平滑性、付着性、耐水性および耐候性に優れた繊維強化プラスチック用の型内被覆組成物を提供することができる。 According to the present invention, it is possible to provide a mold inner coating composition for a fiber reinforced plastic having excellent smoothness, adhesiveness, water resistance and weather resistance.
　以下、本発明の実施形態について、詳細に説明する。なお、（メタ）アクリレートは、アクリレートとメタクリレートの両方を表す意味である。 Hereinafter, embodiments of the present invention will be described in detail. In addition, (meth) acrylate means both acrylate and methacrylate.
＜繊維強化プラスチック成形物用の型内被覆組成物＞
　本発明の繊維強化プラスチック成形物用の型内被覆組成物は、少なくとも、ウレタン（メタ）アクリレート（Ａ）、脂環式構造を有する単官能エチレン性不飽和単量体（Ｂ）、該（Ａ）および（Ｂ）と共重合可能である少なくとも１種の単官能エチレン性不飽和単量体（Ｃ）、離型剤（Ｄ）ならびに開始剤（Ｅ）とを含み、該ウレタン（メタ）アクリレート（Ａ）の少なくとも１種は、重量平均分子量が６００以上７０００以下であり、さらに、官能基数が２以上４以下であることを特徴とする。ウレタン（メタ）アクリレートの重量平均分子量が６００以上７０００以下であり、さらに、官能基数が２以上４以下であれば、平滑性に優れるものとなる。 <In-mold coating composition for fiber reinforced plastic molded products>
The mold inner coating composition for the fiber-reinforced plastic molded product of the present invention comprises at least a urethane (meth) acrylate (A), a monofunctional ethylenically unsaturated monomer (B) having an alicyclic structure, and the above (A). ) And (B), the urethane (meth) acrylate containing at least one monofunctional ethylenically unsaturated monomer (C), a mold release agent (D) and an initiator (E). At least one of (A) is characterized in that the weight average molecular weight is 600 or more and 7,000 or less, and the number of functional groups is 2 or more and 4 or less. When the weight average molecular weight of the urethane (meth) acrylate is 600 or more and 7,000 or less, and the number of functional groups is 2 or more and 4 or less, the smoothness is excellent.
＜ウレタン（メタ）アクリレート（Ａ）＞
　本発明のウレタン（メタ）アクリレート（Ａ）は、ジオールとイソシアネートの反応物に（メタ）アクリレート基を付加した化合物であり、特に芳香環を含まない脂肪族ジオールと脂肪族イソシアネートの反応物に、（メタ）アクリレート基を付加した脂肪族（メタ）アクリレートであることが好ましい。 <Urethane (meth) acrylate (A)>
The urethane (meth) acrylate (A) of the present invention is a compound in which a (meth) acrylate group is added to a reaction product of a diol and an isocyanate, and in particular, a reaction product of an aliphatic diol and an aliphatic isocyanate containing no aromatic ring can be used. It is preferably an aliphatic (meth) acrylate to which a (meth) acrylate group is added.
　本発明のウレタン（メタ）アクリレート（Ａ）は、一般的には、ジイソシアネート化合物、ジオール化合物およびヒドロキシル基含有（メタ）アクリレートを、一括混合して反応させることによって得ることができる。また、他の方法として、ジオール化合物とジイソシアネート化合物とを反応させて、１分子あたり１個以上のイソシアネート基を含むウレタンイソシアネート中間体を形成し、ついで、この中間体とヒドロキシル基含有（メタ）アクリレートとを反応させる方法、ジイソシアネート化合物とヒドロキシル基含有（メタ）アクリレートとを反応させて、１分子あたり１個以上のイソシアネート基を含むウレタン（メタ）アクリレート中間体を形成し、ついで、この中間体とジオール化合物とを反応させる方法等が挙げられる。 The urethane (meth) acrylate (A) of the present invention can generally be obtained by collectively mixing and reacting a diisocyanate compound, a diol compound and a hydroxyl group-containing (meth) acrylate. As another method, a diol compound and a diisocyanate compound are reacted to form a urethane isocyanate intermediate containing one or more isocyanate groups per molecule, and then this intermediate and a hydroxyl group-containing (meth) acrylate are formed. A method of reacting with, a diisocyanate compound is reacted with a hydroxyl group-containing (meth) acrylate to form a urethane (meth) acrylate intermediate containing one or more isocyanate groups per molecule, and then with this intermediate. Examples thereof include a method of reacting with a diol compound.
　本発明のジイソシアネート化合物としては、各種公知のものを用いることができ、例えば、１，２－ジイソシアナトエタン、１，２－ジイソシアナトプロパン、１，３－ジイソシアナトプロパン、ヘキサメチレンジイソシアネート、トリメチルヘキサメチレンジイソシアネート、テトラメチレンジイソシアネート、ビス（４－イソシアナトシクロヘキシル）メタン、メチルシクロヘキサン２，４－ジイソシアネート、メチルシクロヘキサン２，６－ジイソシアネート、１，３－ビス（イソシアナトメチル）シクロヘキサン、１，３－ビス（イソシアナトエチル）シクロヘキサン、３－イソシアナトメチル－３，５，５－トリメチルシクロヘキシルイソシアネート等をあげることができる。 As the diisocyanate compound of the present invention, various known diisocyanate compounds can be used, for example, 1,2-diisocyanatoethane, 1,2-diisocyanatopropane, 1,3-diisocyanatopropane, hexamethylene diisocyanate. , Trimethylhexamethylene diisocyanate, tetramethylene diisocyanate, bis (4-isocyanatocyclohexyl) methane, methylcyclohexane 2,4-diisocyanate, methylcyclohexane 2,6-diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, 1, Examples thereof include 3-bis (isocyanatoethyl) cyclohexane and 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate.
　これらジイソシアネートは、単独でもまたそれら相互の混合物として用いても良い。これらの中で好ましいものは、その構造中に環構造を有しているものであり、特に好ましいものは、３－イソシアナトメチル－３，５，５－トリメチルシクロヘキシルイソシアネート、１，３－ビス（イソシアナトメチル）シクロヘキサン、又はビス（４－イソシアナトシクロヘキシル）メタンである。 These diisocyanates may be used alone or as a mixture thereof. Of these, those having a ring structure in the structure are preferable, and those having 3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate and 1,3-bis (3,5,5-trimethylcyclohexylisocyanate) are particularly preferable. Isocyanatomethyl) cyclohexane, or bis (4-isocyanatocyclohexyl) methane.
　本発明のジオール化合物としては、アルキルジオールを挙げることができる。アルキルジオールとしては、例えば、エチレングリコール、１，３－プロパンジオール、プロピレングリコール、２，３－ブタンジオール、１，４－ブタンジオール、２－エチルブタン－１，４－ジオール、１，５－ペンタジオール、１，６－ヘキサンジオール、１，７－ヘプタンジオール、１，８－オクタンジオール、１，９－ノナンジオール、１，１０－デカンジオール、１，９－デカンジオール、１，４－シクロヘキサンジオール、１，４－ジメチロールシクロヘキサン、４，８－ジヒドロキシトリシクロ〔５．２．１．０2,6 〕デカン、４，８－ビス（ヒドロキシメチル）トリシクロ〔５．２．１．０2,6 〕デカン、２，２－ビス（４－ヒドロキシシクロヘキシル）プロパン、２，２－ジエチルプロパン－１，３－ジオール、２，２－ジメチルプロパン－１，３－ジオール、３－メチルペンタン－１，４－ジオール、２，２－ジエチルブタン－１，３－ジオール、４，５－ノナンジオール、および２－ブテン－１，４－ジオール等が挙げられる。 Examples of the diol compound of the present invention include alkyldiols. Examples of the alkyl diol include ethylene glycol, 1,3-propanediol, propylene glycol, 2,3-butanediol, 1,4-butanediol, 2-ethylbutane-1,4-diol, and 1,5-pentadiol. , 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,9-decanediol, 1,4-cyclohexanediol, 1,4-Dimethylolcyclohexane, 4,8-dihydroxytricyclo [5.2.1.0 2,6 ] decane, 4,8-bis (hydroxymethyl) tricyclo [5.2.1.0 2,6] ] Decane, 2,2-bis (4-hydroxycyclohexyl) propane, 2,2-diethylpropane-1,3-diol, 2,2-dimethylpropane-1,3-diol, 3-methylpentane-1,4 -Diol, 2,2-diethylbutane-1,3-diol, 4,5-nonanediol, 2-butene-1,4-diol and the like can be mentioned.
　本発明の脂肪族ウレタン（メタ）アクリレートの製造に使用されるヒドロキシル基含有（メタ）アクリレートとしては、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート、１，４－シクロヘキサンジメタノールモノアクリレート等が挙げられる。 Examples of the hydroxyl group-containing (meth) acrylate used in the production of the aliphatic urethane (meth) acrylate of the present invention include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. ) Acrylate, 1,4-cyclohexanedimethanol monoacrylate and the like.
　脂肪族ウレタン（メタ）アクリレートの末端の（メタ）アクリレート数は、１～６を選択することができるが、２～４が好ましい。
　本発明のウレタン（メタ）アクリレートは、少なくとも１種の重量平均分子量は６００～７０００が好ましい。重量平均分子量はサイズ排除クロマトグラフィーで測定できる。なお、標準物質にはポリスチレンが使用される。 The number of (meth) acrylates at the end of the aliphatic urethane (meth) acrylate can be selected from 1 to 6, but is preferably 2 to 4.
The urethane (meth) acrylate of the present invention preferably has at least one type having a weight average molecular weight of 600 to 7000. The weight average molecular weight can be measured by size exclusion chromatography. In addition, polystyrene is used as a standard substance.
　本発明の脂肪族ウレタン（メタ）アクリレートは、本発明の被覆組成物に含まれるエチレン性不飽和単量体の総量に対して１０～９５質量％含有させることができ、４０～８５質量％含有させるのが好ましい。２種以上を混合して使用することもできる。 The aliphatic urethane (meth) acrylate of the present invention can be contained in an amount of 10 to 95% by mass and 40 to 85% by mass with respect to the total amount of the ethylenically unsaturated monomer contained in the coating composition of the present invention. It is preferable to let it. Two or more types can be mixed and used.
＜脂環式構造を有する単官能エチレン性不飽和単量体（Ｂ）＞
　本発明の脂環式構造を有する単官能エチレン性不飽和単量体（Ｂ）としては、脂環式（メタ）アクリレート、シクロヘキセン、ビニルシクロヘキサン、シクロペンテン、１－メチルシクロヘキセン、シクロヘプテン等のオレフィン等が挙げられるが、脂環式（メタ）アクリレートが好ましく、特に単量体から得られるポリマーのガラス転移温度Ｔｇが８０～２５０℃である脂環式（メタ）アクリレートであることが好ましい。 <Monofunctional ethylenically unsaturated monomer (B) having an alicyclic structure>
Examples of the monofunctional ethylenically unsaturated monomer (B) having an alicyclic structure of the present invention include olefins such as alicyclic (meth) acrylate, cyclohexene, vinylcyclohexane, cyclopentene, 1-methylcyclohexene, and cycloheptene. Although it can be mentioned, an alicyclic (meth) acrylate is preferable, and an alicyclic (meth) acrylate having a glass transition temperature Tg of a polymer obtained from a monomer of 80 to 250 ° C. is particularly preferable.
　本発明のＴｇ８０～２５０℃の脂環式（メタ）アクリレートとしては、イソボルニルアクリレート（Ｔｇ＝９４℃）、イソボルニルメタクリレート（Ｔｇ＝１８０℃）、ジシクロペンタニルアクリレ－ト（Ｔｇ＝１２０℃）、アダマンチルアクリレート（Ｔｇ＝１５３℃）、アダマンチルメタクリレート（Ｔｇ≒２５０℃）等が挙げられる。単官能モノマーが好ましい。本発明のＴｇ８０℃以上の脂環式（メタ）アクリレートは２種以上を混合して使用することもできる。 Examples of the alicyclic (meth) acrylate having a Tg of 80 to 250 ° C. of the present invention include isobornyl acrylate (Tg = 94 ° C.), isobornyl methacrylate (Tg = 180 ° C.), and dicyclopentanyl acrylicate (Tg). = 120 ° C.), adamantyl acrylate (Tg = 153 ° C.), adamantyl methacrylate (Tg ≈250 ° C.) and the like. Monofunctional monomers are preferred. The alicyclic (meth) acrylate having a Tg of 80 ° C. or higher of the present invention can be used as a mixture of two or more.
　本発明の脂環式構造を有する単官能エチレン性不飽和単量体（Ｂ）は、本発明の被覆組成物に含まれるエチレン性不飽和単量体の総量に対して５～５０質量％含有させることができ、１０～４０質量％含有させるのが好ましい。２種以上を混合して使用することもできる。 The monofunctional ethylenically unsaturated monomer (B) having an alicyclic structure of the present invention is contained in an amount of 5 to 50% by mass based on the total amount of the ethylenically unsaturated monomer contained in the coating composition of the present invention. It can be contained, and it is preferable to contain 10 to 40% by mass. Two or more types can be mixed and used.
＜（Ａ）および（Ｂ）と共重合可能な単官能エチレン性不飽和単量体（Ｃ）＞
　本発明の（Ａ）および（Ｂ）と共重合可能な単官能エチレン性不飽和単量体（Ｃ）は、（Ａ）および（Ｂ）と共重合するものであり（Ｂ）と異なるものであれば特に限定はないが、融点（ｍｐ）が０℃以下の芳香族単量体が好ましい。 <Monofunctional ethylenically unsaturated monomer (C) copolymerizable with (A) and (B)>
The monofunctional ethylenically unsaturated monomer (C) copolymerizable with (A) and (B) of the present invention is copolymerized with (A) and (B) and is different from (B). If there is no particular limitation, an aromatic monomer having a melting point (mp) of 0 ° C. or lower is preferable.
　例えばスチレン（－３０℃）、αメチルスチレン（－２３℃）、βメチルスチレン（－２７℃）、ｐ－メチルスチレン（－７７℃）、４－メチルスチレン（－３４℃）、３－エチルスチレン（－１０１℃）、２－エチルスチレン（－７６℃）、ヒドロキシエチルメタクリレート（－１２℃）、ヒドロキシエチルアクリレート（－６０℃）、ヒドロキシプロピルメタクリレート（－５８℃）等が挙げられる。 For example, styrene (-30 ° C), α-methylstyrene (-23 ° C), β-methylstyrene (-27 ° C), p-methylstyrene (-77 ° C), 4-methylstyrene (-34 ° C), 3-ethylstyrene. (-101 ° C.), 2-ethylstyrene (-76 ° C.), hydroxyethyl methacrylate (-12 ° C.), hydroxyethyl acrylate (-60 ° C.), hydroxypropyl methacrylate (-58 ° C.) and the like.
　またヒドロキシ基含有単量体が好ましく、本発明の脂肪族ウレタン（メタ）アクリレートの製造に使用されるヒドロキシル基含有（メタ）アクリレートを、そのまま使用することができる。本発明のヒドロキシアルキル（メタ）アクリレートは２種以上を混合して使用することもできる。 Further, a hydroxy group-containing monomer is preferable, and the hydroxyl group-containing (meth) acrylate used in the production of the aliphatic urethane (meth) acrylate of the present invention can be used as it is. The hydroxyalkyl (meth) acrylate of the present invention can also be used by mixing two or more kinds.
　本発明の（Ｃ）は、本発明の被覆組成物に含まれるエチレン性不飽和単量体の総量に対して１～３０質量％含有させることができ、５～２０質量％含有させるのが好ましい。２種以上を混合して使用することもできる。 The (C) of the present invention can be contained in an amount of 1 to 30% by mass, preferably 5 to 20% by mass, based on the total amount of the ethylenically unsaturated monomer contained in the coating composition of the present invention. .. Two or more types can be mixed and used.
＜（Ａ），（Ｂ）、（Ｃ）の関係＞
　本発明のウレタン（メタ）アクリレート（Ａ）、前記脂環式構造を有する単官能エチレン性不飽和単量体（Ｂ）および前記単官能エチレン性不飽和単量体（Ｃ）が、前記組成物に含まれるエチレン性不飽和単量体の総量に対してそれぞれ４０～８５質量％、１０～４０質量％および５～２０質量％含有されることが好ましい。 <Relationship between (A), (B), and (C)>
The composition of the urethane (meth) acrylate (A) of the present invention, the monofunctional ethylenically unsaturated monomer (B) having the alicyclic structure, and the monofunctional ethylenically unsaturated monomer (C). It is preferable that the ethylenically unsaturated monomer is contained in an amount of 40 to 85% by mass, 10 to 40% by mass, and 5 to 20% by mass, respectively, based on the total amount of the ethylenically unsaturated monomer.
　（Ａ）をこの範囲とすることにより耐候性、付着性に優れたものとなり、（Ｂ）をこの範囲とすることにより耐湿性、クラック抑制性に優れたものとなり、（Ｃ）をこの範囲とすることにより、（Ａ）、（Ｂ）との混和性が良好となり、液の安定性が優れたものとなる。また、前記組成物に含まれるエチレン性不飽和単量体の総量に対する（Ａ）と（Ｂ）と（Ｃ）の合計量を８０～１００質量％の範囲とすることにより、平滑性に優れるものとなる。 By setting (A) in this range, weather resistance and adhesion are excellent, and by setting (B) in this range, moisture resistance and crack suppression are excellent, and (C) is in this range. By doing so, the miscibility with (A) and (B) becomes good, and the stability of the liquid becomes excellent. Further, by setting the total amount of (A), (B) and (C) with respect to the total amount of the ethylenically unsaturated monomer contained in the composition in the range of 80 to 100% by mass, the smoothness is excellent. It becomes.
　さらには、脂環式構造を有する単官能エチレン性不飽和単量体（Ｂ）と単官能エチレン性不飽和単量体（Ｃ）のうち、溶解度パラメーターＳＰ値が９．５以下のものが前記組成物に含まれるエチレン性不飽和単量体の総量に対して５～６０質量％含まれていることが基材への付着性が優れたものとなり好ましい。 Further, among the monofunctional ethylenically unsaturated monomer (B) and the monofunctional ethylenically unsaturated monomer (C) having an alicyclic structure, those having a solubility parameter SP value of 9.5 or less are described above. It is preferable that the ethylenically unsaturated monomer contained in the composition is contained in an amount of 5 to 60% by mass based on the total amount of the ethylenically unsaturated monomer because the adhesion to the substrate is excellent.
　本発明におけるＳＰ値の計算方法について以下に示す。ＳＰ値とは樹脂組成に固有の数値であって相溶性を判断する際の目安となるもので、種々の計算方法や実測方法があるが、本発明においては、Hoyの提唱した蒸気圧法によるＳＰ値を用いて求めた分子引力定数を使用し、文献ケイ・エル・ホイ、ジェイ・ペイント・テクノロジー、４２、[５４１]、７６（１９７０）（K. L. Hoy, J. Paint Technology, 42, [541], 76(1970)）に記載された方法に準拠して計算した値を意味する。 The calculation method of the SP value in the present invention is shown below. The SP value is a numerical value peculiar to the resin composition and serves as a guide for determining compatibility. There are various calculation methods and actual measurement methods, but in the present invention, SP by the vapor pressure method proposed by Hoy is used. Using the molecular attraction constants obtained using the values, the literature K.L. Hoy, J. Paint Technology, 42, [541], 76 (1970) (K. L. Hoy, J. Paint Technology, 42, It means a value calculated according to the method described in [541], 76 (1970)).
　具体的には、ＳＰ値は、δ＝（ｄΣＧ）／Ｍで表され、ｄはポリマーの密度、Ｍはポリマーの基本構造単位の分子量、ΣＧは該基本構造単位中に存在する原子（団）に対応する分子引力定数Ｇの総和である。 Specifically, the SP value is represented by δ = (dΣG) / M, where d is the density of the polymer, M is the molecular weight of the basic structural unit of the polymer, and ΣG is the atom (group) existing in the basic structural unit. It is the sum of the molecular attractive force constants G corresponding to.
＜離型剤（Ｄ）＞
　本発明で使用される離型剤（Ｄ）は、硬化被膜が金型からスムーズに離型するために添加するものであるが、その種類としては亜鉛、アルミニウム、マグネシウム、カルシウムなどのステアリン酸塩やレシチン、アルキルフォスフェート等が代表的なものとして挙げられるが、これらに限定されるものではない。なお離型剤（Ｄ）は、被覆組成物中０．０５～４質量％配合するのが好ましい。 <Release agent (D)>
The mold release agent (D) used in the present invention is added so that the cured film can be smoothly released from the mold, and the types thereof are stearates such as zinc, aluminum, magnesium, and calcium. , Lecithin, alkyl phosphate, etc. are typical examples, but the present invention is not limited to these. The release agent (D) is preferably blended in an amount of 0.05 to 4% by mass in the coating composition.
＜開始剤（Ｅ）＞
　本発明で使用される重合開始剤（Ｅ）は、フリーラジカルを発生し、前記単量体成分を重合させ、被膜を硬化させるために配合する。重合開始剤としては、ターシャリーブチルパーベンゾエイト、ターシャリーブチルパーオクトエイト、メチルエチルケトンパーオキサイド、ターシャリーベンジルペルベンゾエート、ジクミルペルオキシド、クミルハイドロパーオキサイド、過酸化ジアセチル、過酸化カプリリル、ターシャリーブチルハイドロパーオキサイド等が代表的なものとして挙げられるが、これらに限定されるものではない。重合開始剤（Ｅ）は、前記単量体成分に対し０.１～５質量％配合するのが好ましい。 <Initiator (E)>
The polymerization initiator (E) used in the present invention is blended to generate free radicals, polymerize the monomer component, and cure the coating film. As polymerization initiators, tertiary butyl perbenzoate, tertiary butyl peroctate, methyl ethyl ketone peroxide, tertiary benzyl perbenzoate, dicumyl peroxide, cumyl hydroperoxide, diacetyl peroxide, caprylyl peroxide, tertiary Butyl hydroperoxide and the like are typical examples, but the present invention is not limited thereto. The polymerization initiator (E) is preferably blended in an amount of 0.1 to 5% by mass based on the monomer component.
＜その他の添加剤＞
　本発明の被覆組成物は、さらに必要に応じ顔料や硬化促進剤、分散剤、沈降防止剤、流動助剤、重合禁止剤、紫外線吸収剤等の各種添加剤を含有することができる。 <Other additives>
The coating composition of the present invention can further contain various additives such as pigments, curing accelerators, dispersants, sedimentation inhibitors, flow aids, polymerization inhibitors, and ultraviolet absorbers, if necessary.
　顔料は、クリヤーの場合、必ずしも配合する必要ないが、成形物を着色し、美観をもたせたり、被膜硬化に伴う収縮応力を分散させ、成形物との付着性を向上させたり、成形物表面に存在する巣穴等を充填し、表面の微小な凹凸を平滑にしたり、さらには導電性等の機能をもたせる目的で含有することができる。 In the case of clear, the pigment does not necessarily have to be blended, but it colors the molded product to give it an aesthetic appearance, disperses the shrinkage stress associated with the curing of the film, improves the adhesion to the molded product, and on the surface of the molded product. It can be contained for the purpose of filling existing burrows and the like, smoothing minute irregularities on the surface, and further providing functions such as conductivity.
　なお、顔料は、被膜の硬化性に悪影響を及ぼさず、変色しにくいものであれば、従来から通常プラスチック用、塗料用に使用されている着色顔料、体質顔料を特に制限なく用いることが出来る。 As the pigment, as long as it does not adversely affect the curability of the film and is resistant to discoloration, coloring pigments and extender pigments that have been conventionally used for plastics and paints can be used without particular limitation.
　着色顔料の具体例としては、白色系では酸化チタン、黄色系ではベンジジンイエロー、チタンイエロー、ハンザイエロー；橙色系ではモリブデートオレンジ、黄鉛、ベンジジンオレンジ；赤色系ではキナクリドン、マルーン；黒色系ではカーボンブラック、酸化鉄等の粉末状顔料あるいはフレーク状のアルミニウム、銅、ステンレス、マイカ、グラファイト、窒化チタニウム等の鱗片状顔料を代表的なものとして挙げることができる。 Specific examples of coloring pigments include titanium oxide for whites, benzidine yellow, titanium yellow, and Hansa yellow for yellows; molybdate orange, chrome yellow, and benzidine oranges for oranges; quinacridone and maroon for reds; carbon for blacks. Typical examples include powder pigments such as black and iron oxide, and flaky pigments such as flaky aluminum, copper, stainless steel, mica, graphite, and titanium nitride.
　また体質顔料としては炭酸カルシウム、タルク、硫酸バリウム、水酸化アルミニウム、クレー、各種樹脂粉末等を代表的なものとして挙げることができる。顔料は前記目的に応じ被覆組成物中任意な量を含有することが可能であるが、通常着色顔料の場合、４０質量％まで、体質顔料の場合５０室量％までが適当であり、両者を併用する場合は６５質量％まで含有するのが好ましい。 Calcium carbonate, talc, barium sulfate, aluminum hydroxide, clay, various resin powders, etc. can be mentioned as typical extender pigments. The pigment can be contained in an arbitrary amount in the coating composition depending on the above-mentioned purpose, but usually up to 40% by mass in the case of a coloring pigment and up to 50% by mass in the case of an extender pigment, both of which are suitable. When used in combination, it is preferably contained up to 65% by mass.
＜被覆組成物を型内被覆する方法＞
　本発明で使用する繊維強化プラスチック成形物は、ＳＭＣ、ＢＭＣ、ＦＲＴＰ、スタンパブルシート等の従来から公知のものが特に制限なく利用出来る。具体的には不飽和ポリエステル樹脂系、エポキシアクリレート樹脂系、フェノール樹脂系、エポキシ樹脂系等の熱硬化性樹脂あるいはポリオレフィン樹脂系、ポリスチレン樹脂系、ポリカーボネート樹脂系等の熱可塑性樹脂をマトリックスとする、繊維強化プラスチック成形物が代表的なものとして挙げられる。 <Method of coating the coating composition in the mold>
As the fiber reinforced plastic molded product used in the present invention, conventionally known ones such as SMC, BMC, FRTP, and stampable sheet can be used without particular limitation. Specifically, a heat-curable resin such as unsaturated polyester resin-based, epoxy acrylate resin-based, phenol resin-based, or epoxy resin-based or thermoplastic resin such as polyolefin resin-based, polystyrene resin-based, or polycarbonate resin-based is used as a matrix. A typical example is a fiber-reinforced plastic molded product.
　繊維強化プラスチック成形物に使用される繊維としては、ガラス繊維、炭素繊維、有機繊維、ミネラル繊維が挙げられるが、特に炭素繊維で強化されたプラスチック成形物に対しても、本発明の被覆組成物を好適に適用できる。 Examples of the fiber used in the fiber-reinforced plastic molded product include glass fiber, carbon fiber, organic fiber, and mineral fiber. In particular, the coating composition of the present invention is also applied to a plastic molded product reinforced with carbon fiber. Can be preferably applied.
　成形方法としては金型内で成形する従来の方法が特に制限なく利用出来るが、好適には特開平５－７０７１２号公報に記載の方法がある。すなわち、一方の金型が他方の金型（以下、便宜上前者を「下型」、後者を「上型」という。）内に嵌合することにより、目的とする成形物の形状を有するキャビティー空間を形成する金型内に炭素繊維強化プラスチック成形物を入れ、嵌合せ金型内で成形する。 As a molding method, a conventional method of molding in a mold can be used without particular limitation, but there is preferably a method described in JP-A-5-70712. That is, a cavity having the shape of the target molded product by fitting one mold into the other mold (hereinafter, for convenience, the former is referred to as "lower mold" and the latter is referred to as "upper mold"). A carbon fiber reinforced plastic molded product is placed in a mold that forms a space, and is fitted and molded in the mold.
　すなわち成形物が熱硬化性樹脂をマトリックスとしている場合は、金型内で加熱・加圧し、成形物をフローさせるとともに熱硬化反応させ、目的とする形状に成形する。成形加熱温度は、成形時間、成形物の種類等により任意に決定されるが通常１３０～２００℃が好ましく、成形物を入れる前に予め金型を前記温度にセットし、所望の硬化被膜が得られるまで該温度に維持するようにしておくのが望ましい。 That is, when the molded product uses a thermosetting resin as a matrix, it is heated and pressurized in the mold to allow the molded product to flow and undergo a thermosetting reaction to form the desired shape. The molding heating temperature is arbitrarily determined depending on the molding time, the type of the molded product, etc., but is usually preferably 130 to 200 ° C., and the mold is set to the above temperature in advance before inserting the molded product to obtain a desired cured film. It is desirable to keep the temperature at that temperature until
　成形圧力は、加熱温度、成形物の種類等により任意に決定されるが、通常 ５～２０ＭＰａが好ましい。成形時間は、成形物が完全に熱硬化反応完了するまででもよいが後述する被覆組成物を注入した際、成形物の形状を損なわない程度の強度に硬化していればよく、通常４０～２００秒程度が好ましい。 The molding pressure is arbitrarily determined depending on the heating temperature, the type of molded product, etc., but is usually preferably 5 to 20 MPa. The molding time may be until the molded product completely completes the thermosetting reaction, but when the coating composition described later is injected, the molded product may be cured to a strength that does not impair the shape of the molded product, and is usually 40 to 200. About seconds is preferable.
　一方成形物が熱可塑性樹脂をマトリックスとしている場合は、あらかじめ加熱オーブン等により加熱軟化させた材料を金型内で加圧し、成形物をフローさせるとともに目的とする形状に成形し、後述する被覆組成物を注入した際、成形物の形状が損わない程度の強度に硬化させる。 On the other hand, when the molded product uses a thermoplastic resin as a matrix, the material previously heated and softened by a heating oven or the like is pressed in a mold to allow the molded product to flow and to be molded into a desired shape, and the coating composition described later. When the product is injected, it is cured to a strength that does not damage the shape of the molded product.
　このようにして成形物を硬化させた後、上型を成形物の表面から、分離して後述する所望の硬化被膜厚よりも大きいが、前記金型の嵌合を離脱させるには不十分なギャップを与えた後、もしくは金型を嵌合した状態で前記成形圧力を維持したまま、又は該圧力を減圧した後、所望の膜厚、好ましくは１０～１０００μｍの硬化被膜が得られるだけの量の被覆組成物を上型と成形物表面の間に注入（射出注入）する。 After the molded product is cured in this manner, the upper mold is separated from the surface of the molded product, which is larger than the desired cured film thickness to be described later, but is insufficient to release the fitting of the mold. An amount sufficient to obtain a desired film thickness, preferably 10 to 1000 μm, after giving a gap, maintaining the molding pressure with the mold fitted, or reducing the pressure. The coating composition of is injected (injection injection) between the upper mold and the surface of the molded product.
　次いで、成形物が熱硬化性樹脂をマトリックスとしている場合は、加熱温度を前記温度にほぼ保持しながら、被覆組成物が均一に成形物表面を覆い、浸透するよう約 １～１４ＭＰａに（再）加圧し、硬化被膜が形成するまで、通常約３０～１２０秒程度維持する。 Next, when the molded product uses a thermosetting resin as a matrix, the coating composition uniformly covers the surface of the molded product and permeates the molded product while maintaining the heating temperature at about 1 to 14 MPa (re). The pressure is usually maintained for about 30 to 120 seconds until a cured film is formed.
　一方成形物が熱可塑性樹脂をマトリックスとしている場合は、成形物が再軟化せず、かつ被覆組成物が硬化する温度、例えば６０～１６０℃に金型温度を保持しながら、被覆組成物が均一に成形物表面を覆い、浸透するよう約 １～１４ＭＰａに（再）加圧し、硬化被膜が形成するまで、通常約３０～１５０秒程度維持する。なお、この場合は、被覆組成物の硬化温度か低い程望ましいのでナフテン酸コバルト、アミン等の硬化促進剤を併用してもよい。 On the other hand, when the molded product uses a thermoplastic resin as a matrix, the coating composition is uniform while maintaining the mold temperature at a temperature at which the molded product does not resoften and the coating composition cures, for example, 60 to 160 ° C. The surface of the molded product is covered and (re) pressurized to about 1 to 14 MPa so as to penetrate, and usually maintained for about 30 to 150 seconds until a cured film is formed. In this case, the lower the curing temperature of the coating composition, the more desirable it is, so a curing accelerator such as cobalt naphthenate or amine may be used in combination.
　このようにして成形物表面に硬化被膜が形成された後、金型を開き、成形物を取り出すことにより、保護被膜を有する成形物が得られる。 After the cured film is formed on the surface of the molded product in this way, the mold is opened and the molded product is taken out to obtain a molded product having a protective film.
＜実施例１～３及び比較例１～２＞
　表１に記載の各成分を混合し、実施例１～１２、比較例１～４の型内被覆組成物を調製した。型内被覆組成物の原料を以下に示す。
　［ウレタン（メタ）アクリレート（Ａ）］
・ウレタンアクリレート１「ＥＢＥＣＲＹＬ８４０２」（ダイセル・オルネクス株式会社製、重量平均分子量１０００、官能基数：２）
・ウレタンアクリレート２「ＥＢＥＣＲＹＬ８４０９」（ダイセル・オルネクス株式会社製、重量平均分子量１０００、官能基数：２）
・ウレタンアクリレート３「ＥＢＥＣＲＹＬ４５１３」（ダイセル・オルネクス株式会社製、重量平均分子量２０００、官能基数：３）
・ウレタンアクリレート５「ＣＮ９００１ＮＳ」（Ｓａｒｔｏｍｅｒ　Ａｒｋｅｍａ　Ｇｒｐｕｐ社製、重量平均分子量５０００、官能基数：２） <Examples 1 to 3 and Comparative Examples 1 to 2>
Each component shown in Table 1 was mixed to prepare mold inner coating compositions of Examples 1 to 12 and Comparative Examples 1 to 4. The raw materials of the mold inner coating composition are shown below.
[Urethane (meth) acrylate (A)]
-Urethane acrylate 1 "EBECRYL8402" (manufactured by Daicel Ornex Co., Ltd., weight average molecular weight 1000, number of functional groups: 2)
-Urethane acrylate 2 "EBECRYL8409" (manufactured by Daicel Ornex Co., Ltd., weight average molecular weight 1000, number of functional groups: 2)
-Urethane acrylate 3 "EBECRYL4513" (manufactured by Daicel Ornex Co., Ltd., weight average molecular weight 2000, number of functional groups: 3)
-Urethane acrylate 5 "CN9001NS" (manufactured by Sartomer Arkema Grpup, weight average molecular weight 5000, number of functional groups: 2)
　［脂環式構造を有する単官能エチレン性不飽和単量体（Ｂ）］
・イソボルニルアクリレート（共栄社化学株式会社製、官能基数：１、Ｔｇ＝９４℃、ＳＰ値＝８．８７）
・イソボルニルメタクリレート（共栄社化学株式会社製、官能基数：１、Ｔｇ＝１８０℃、ＳＰ値＝８．７６）
・ジシクロペンタニルアクリレート（日立化成株式会社製、官能基数：１、Ｔｇ＝１２０℃、ＳＰ値＝８．８１）
・アダマンチルメタクリレート（大阪有機化学工業株式会社製、官能基数：１、Ｔｇ＝２５０℃、ＳＰ値＝９．１４） [Monofunctional ethylenically unsaturated monomer (B) having an alicyclic structure]
-Isobornyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd., number of functional groups: 1, Tg = 94 ° C., SP value = 8.87)
-Isobornyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd., number of functional groups: 1, Tg = 180 ° C., SP value = 8.76)
-Dicyclopentanyl acrylate (manufactured by Hitachi Chemical Company, Ltd., number of functional groups: 1, Tg = 120 ° C., SP value = 8.81)
-Adamantyl methacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., number of functional groups: 1, Tg = 250 ° C., SP value = 9.14)
　［（Ａ）および（Ｂ）と共重合可能である少なくとも1種の単官能エチレン性不飽和単量体（Ｃ）］
・スチレン（ＳＰ値＝９．０９）
・ヒドロキシプロピルメタクリレート（ＳＰ値＝１０．６８）
・ヒドロキシエチルメタクリレート（ＳＰ値＝１１．５５）
　［その他のエチレン性不飽和単量体］
・ウレタンアクリレート４「ＫＲＭ８２００」（ダイセル・オルネクス株式会社製、重量平均分子量１０００、官能基数：６）
・エポキシアクリレート「ＥＢＥＣＲＹＬ６００」（ダイセル・オルネクス株式会社製、重量平均分子量５００、官能基数：２） [At least one monofunctional ethylenically unsaturated monomer (C) copolymerizable with (A) and (B)]
・ Styrene (SP value = 9.09)
-Hydroxypropyl methacrylate (SP value = 10.68)
-Hydroxyethyl methacrylate (SP value = 11.55)
[Other ethylenically unsaturated monomers]
-Urethane acrylate 4 "KRM8200" (manufactured by Daicel Ornex Co., Ltd., weight average molecular weight 1000, number of functional groups: 6)
-Epoxy acrylate "EBECRYL600" (manufactured by Daicel Ornex Co., Ltd., weight average molecular weight 500, number of functional groups: 2)
　［離型剤（Ｄ）］
・ステアリン酸亜鉛
　［開始剤（Ｅ）］
・t-ブチル過酸化ベンゾイル「カヤブチルＢ」（化薬アクゾ株式会社製） [Release agent (D)]
-Zinc stearate [Initiator (E)]
・ T-Butyl Benzoyl peroxide "Kayabutyl B" (manufactured by Kayaku Akzo Corporation)
　≪型内被覆成形体の製造≫
　長さ２５０ｍｍ、巾１５０ｍｍ、高さ１０ｍｍ、板厚２ｍｍの箱形状の樹脂成形体を得るためのキャビティーを有するクロムメッキを施した箱型試験金型を用い、成形温度を上型１５０℃、下型１５０℃に設定した。まず、下型上にエポキシアクリレート系熱硬化性炭素繊維強化プラスチック成形材料（炭素繊維含有量５０質量％）であるＳＭＣ材料を１５０ｇセットし、成形圧９ＭＰａ 、成形時間６０秒の条件下で成形した。
　次いで成型圧を減圧させた後、前記各被覆組成物１０ｇを上型と成形物間に注入し、成形圧６ＭＰａに加圧し、１２０秒間維持した。次いで金型を開き、成形物を取り出した。その結果、被膜（膜厚約１００μｍ）で覆われた成形物が得られた。 ≪Manufacturing of mold inner coating molded product≫
Using a chrome-plated box-type test mold having a cavity for obtaining a box-shaped resin molded product having a length of 250 mm, a width of 150 mm, a height of 10 mm, and a plate thickness of 2 mm, the molding temperature was set to 150 ° C. The lower mold was set to 150 ° C. First, 150 g of SMC material, which is an epoxy acrylate-based thermosetting carbon fiber reinforced plastic molding material (carbon fiber content 50% by mass), was set on the lower mold and molded under the conditions of a molding pressure of 9 MPa and a molding time of 60 seconds. ..
Next, after reducing the molding pressure, 10 g of each of the coating compositions was injected between the upper mold and the molded product, and the molding pressure was pressurized to 6 MPa and maintained for 120 seconds. Then the mold was opened and the molded product was taken out. As a result, a molded product covered with a coating film (thickness of about 100 μm) was obtained.
＜型内被覆成形体の評価＞
　得られた型内被覆成形体に対して、基材と被覆膜との付着性、被覆成形体の耐候性、耐湿性及び平滑性を下記の試験方法により測定した。それらの結果を表１、２に示す。 <Evaluation of mold inner coating molded product>
The adhesiveness between the base material and the coating film, the weather resistance, the moisture resistance and the smoothness of the coated molded product were measured with respect to the obtained in-mold coated molded product by the following test method. The results are shown in Tables 1 and 2.
　≪１．基材と被覆膜との付着性≫
　得られた型内被覆成形体について、ＪＩＳ　Ｋ　５６００－５－６：１９９９（付着性（クロスカット法））に従って付着性試験を実施した。カットの間隔は２ｍｍとし、碁盤目１００個におけるセロテープ剥離試験による塗膜外観を目視で評価した。
　被覆膜の付着性はＪＩＳ　Ｋ　５６００－５－６に記載の試験結果の分類に基づき下記の０～５の６段階で評価した。なお、評価は各５ヶ所で行い結果を平均値で表示した。
・分類０：カットの縁が完全に滑らかで、どの格子の目にもはがれがない。
・分類１：積層塗膜の残存率が９５～９９％。
・分類２：積層塗膜の残存率が８５％以上９５％未満。
・分類３：積層塗膜の残存率が６５％以上８５％未満。
・分類４：積層塗膜の残存率が０％以上６５％未満。
・分類５：分類４でも分類できないはがれ程度。 ≪1. Adhesion between the base material and the coating film ≫
The obtained mold inner coating molded product was subjected to an adhesion test according to JIS K 5600-5-6: 1999 (adhesion (cross-cut method)). The interval between cuts was 2 mm, and the appearance of the coating film by the cellophane tape peeling test on 100 grids was visually evaluated.
The adhesiveness of the coating film was evaluated on a scale of 0 to 5 below based on the classification of the test results described in JIS K 5600-5-6. The evaluation was performed at 5 locations each, and the results were displayed as average values.
-Category 0: The edges of the cut are completely smooth, and there is no peeling in the eyes of any grid.
-Category 1: The residual rate of the laminated coating film is 95 to 99%.
-Category 2: The residual rate of the laminated coating film is 85% or more and less than 95%.
-Category 3: The residual rate of the laminated coating film is 65% or more and less than 85%.
-Category 4: The residual rate of the laminated coating film is 0% or more and less than 65%.
-Category 5: Degree of peeling that cannot be classified even in Category 4.
　≪２．促進耐候性≫
　得られた型内被覆成形体について、ＪＩＳ　Ｋ　５６００－７－７：２００８に記載のキセノンランプ法に従い、ウェザオメーターＣｉ４０００（アトラス社製）により促進耐侯性試験を実施した。放射露光量が５００ＭＪに達するまで実施し、塗膜外観を目視で評価した。なお、評価基準は以下の通りである。
　合格：フクレ又は光沢低下が発生しない。
　不合格：フクレ又は光沢低下が発生する。 ≪2. Accelerated weather resistance ≫
The obtained mold inner coating molded product was subjected to an accelerated weather resistance test by a weather meter Ci4000 (manufactured by Atlas) according to the xenon lamp method described in JIS K 5600-7-7: 2008. This was carried out until the radiation exposure amount reached 500 MJ, and the appearance of the coating film was visually evaluated. The evaluation criteria are as follows.
Pass: No blistering or gloss loss occurs.
Fail: Blisters or gloss loss occur.
　≪３．被覆成形体の耐湿性≫
　得られた型内被覆成形体について、ＪＩＳ　Ｋ　５６００－７－２：１９９９に従って、耐湿性試験（試験条件は、８０±１℃、相対湿度９５％以上、試験時間４８時間）を実施した。評価は、試験直後及び室内２時間静置した後の観察によって、被覆膜にしわ、膨れ、割れ、さび及びはがれ等が認められず、２時間静置した後の塗膜外観を目視で評価した。
　合格　：くもり、白化及び変色等がない。
　不合格：くもり、白化及び変色等が認められる。 ≪3. Moisture resistance of coated part ≫
The obtained mold inner coating molded product was subjected to a moisture resistance test (test conditions: 80 ± 1 ° C., relative humidity 95% or more, test time 48 hours) according to JIS K 5600-7-2: 1999. In the evaluation, wrinkles, swelling, cracks, rust, peeling, etc. were not observed in the coating film by observation immediately after the test and after standing in the room for 2 hours, and the appearance of the coating film after standing for 2 hours was visually evaluated. did.
Passed: No cloudiness, whitening or discoloration.
Fail: Cloudy, whitening, discoloration, etc. are observed.
　≪４．被覆成形体の平滑性≫
　得られた型内被覆成形体を金型から取り出し、室内に２時間静置した後の目視による観察によって、塗膜が平滑であれば“合格”、平滑性なしや光沢ムラなどの異常が認められるときは“不合格”とした。 ≪4. Smoothness of coated part ≫
The obtained inner-coated molded product was taken out of the mold and allowed to stand indoors for 2 hours, and then visually observed. If the coating film was smooth, "passed", and abnormalities such as no smoothness and uneven gloss were observed. When it was done, it was judged as "failed".
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　表１、２の結果から明らかなように、本発明の型内被覆組成物は、付着性、耐候性、耐湿および平滑性に優れている。 As is clear from the results in Tables 1 and 2, the mold inner coating composition of the present invention is excellent in adhesion, weather resistance, moisture resistance and smoothness.

Claims (4)

  1. 　少なくとも、ウレタン（メタ）アクリレート（Ａ）と脂環式構造を有する単官能エチレン性不飽和単量体（Ｂ）、該（Ａ）および（Ｂ）と共重合可能である少なくとも1種の単官能エチレン性不飽和単量体（Ｃ）、離型剤（Ｄ）ならびに開始剤（Ｅ）とを含み、
    該ウレタン（メタ）アクリレート（Ａ）の少なくとも１種は、重量平均分子量が６００以上７０００以下であり、さらに、官能基数が２以上４以下であることを特徴とする繊維強化プラスチック成形物用の型内被覆組成物。     At least a monofunctional ethylenically unsaturated monomer (B) having an alicyclic structure with a urethane (meth) acrylate (A), and at least one monofunctional copolymerizable with the (A) and (B). It contains an ethylenically unsaturated monomer (C), a mold release agent (D) and an initiator (E).
    At least one of the urethane (meth) acrylates (A) has a weight average molecular weight of 600 or more and 7,000 or less, and further has a functional group number of 2 or more and 4 or less, which is a mold for a fiber reinforced plastic molded product. Inner coating composition.
  2. 　前記ウレタン（メタ）アクリレート（Ａ）、前記脂環式構造を有する単官能エチレン性不飽和単量体（Ｂ）および前記単官能エチレン性不飽和単量体（Ｃ）が、前記組成物に含まれるエチレン性不飽和単量体の総量に対して、それぞれ４０～８５質量％、１０～４０質量％および５～２０質量％含有されることを特徴とする請求項１に記載の繊維強化プラスチック成形物用の型内被覆組成物。 The composition contains the urethane (meth) acrylate (A), the monofunctional ethylenically unsaturated monomer (B) having an alicyclic structure, and the monofunctional ethylenically unsaturated monomer (C). The fiber-reinforced plastic molding according to claim 1, which contains 40 to 85% by mass, 10 to 40% by mass, and 5 to 20% by mass, respectively, with respect to the total amount of the ethylenically unsaturated monomer. Mold inner coating composition for objects.
  3. 　前記脂環式構造を有する単官能エチレン性不飽和単量体（Ｂ）から得られるポリマーのガラス転移温度Ｔｇが８０～２５０℃であることを特徴とする請求項１又は２に記載の繊維強化プラスチック成形物用の型内被覆組成物。 The fiber reinforced according to claim 1 or 2, wherein the glass transition temperature Tg of the polymer obtained from the monofunctional ethylenically unsaturated monomer (B) having an alicyclic structure is 80 to 250 ° C. In-mold coating composition for plastic moldings.
  4. 　前記脂環式構造を有する単官能エチレン性不飽和単量体（Ｂ）と単官能エチレン性不飽和単量体（Ｃ）のうち、溶解度パラメーターＳＰ値が９．５以下のものが、前記組成物に含まれるエチレン性不飽和単量体の総量に対して５～６０質量％含まれていることを特徴とする請求項１～３のいずれかに記載の繊維強化プラスチック成形物用の型内被覆組成物。 Of the monofunctional ethylenically unsaturated monomer (B) and the monofunctional ethylenically unsaturated monomer (C) having an alicyclic structure, those having a solubility parameter SP value of 9.5 or less have the composition. The in-mold for a fiber-reinforced plastic molded product according to any one of claims 1 to 3, wherein the ethylenically unsaturated monomer is contained in an amount of 5 to 60% by mass based on the total amount of the ethylenically unsaturated monomer. Coating composition.
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