JP7372805B2 - Coating film for housing and photocurable coating resin composition for housing - Google Patents

Coating film for housing and photocurable coating resin composition for housing Download PDF

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JP7372805B2
JP7372805B2 JP2019178846A JP2019178846A JP7372805B2 JP 7372805 B2 JP7372805 B2 JP 7372805B2 JP 2019178846 A JP2019178846 A JP 2019178846A JP 2019178846 A JP2019178846 A JP 2019178846A JP 7372805 B2 JP7372805 B2 JP 7372805B2
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photocurable
housing
coating film
resin composition
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JP2021054934A (en
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正義 磯崎
憲 齋藤
俊宏 河谷
亮 森
研二 梅田
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Nippon Steel Chemical and Materials Co Ltd
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Priority to CN202011039546.XA priority patent/CN112574456B/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/103—Esters of polyhydric alcohols or polyhydric phenols of trialcohols, e.g. trimethylolpropane tri(meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/104—Esters of polyhydric alcohols or polyhydric phenols of tetraalcohols, e.g. pentaerythritol tetra(meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
    • C08J2333/12—Homopolymers or copolymers of methyl methacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2435/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Derivatives of such polymers
    • C08J2435/02—Characterised by the use of homopolymers or copolymers of esters

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Paints Or Removers (AREA)
  • Laminated Bodies (AREA)

Description

本発明はスマートフォンに代表される携帯通信機器の筐体用として優れた特性を発現する筐体用コーティング膜および光硬化性コーティング樹脂組成物に関する。 The present invention relates to a coating film for housings and a photocurable coating resin composition that exhibits excellent properties for housings of mobile communication devices such as smartphones.

近年、スマートフォンや携帯電話、通信機能付きのタブレット端末など携帯性に優れた端末機器が広く普及している。
このような通信機器においては、通信速度、送受信データ量の増大に対応しミリ波など高周波帯域における通信手段が現実となってきており、データ送受信におけるノイズ、伝送損失などによる通信エラーの低減が緊急の課題となっている。
その対応手段として、上記端末機器の筐体として低誘電特性に優れたプラスチック筐体の採用が検討されている。プラスチック筐体は優れた低誘電特性の他に、加工性、量産性、コストパフォーマンスに優れることからミドルエンドからハイエンドの端末機器に採用が広がろうとしている。
一方、プラスチック筐体には表面が傷つきやすく、ガラス、金属筐体に比べて外観の高級感に劣るという欠点を有している。そのため、プラスチック筐体の表面にコーティングを設ける手法が用いられている。
こうしたコーティングにはアクリル系の樹脂が多く用いられており、活性光線の照射により光硬化することで優れた表面硬度（耐スチールウール性）を発現している。
プラスチック筐体用のコーティング層として、下記特許文献１、２には耐擦傷性を満足するために機能性を有したハードコート層を転写する方法が提案されている。特許文献２～４ではケイ素化合物を用いることで、滑り性、離形性、可とう性（柔軟性）および応力緩和により耐スチールウール性を得ている。 In recent years, highly portable terminal devices such as smartphones, mobile phones, and tablet terminals with communication functions have become widespread.
In such communication devices, communication methods using high frequency bands such as millimeter waves have become a reality in response to increases in communication speed and the amount of transmitted and received data, and it is urgent to reduce communication errors caused by noise, transmission loss, etc. during data transmission and reception. This has become an issue.
As a means to address this issue, consideration is being given to using plastic casings with excellent low dielectric properties as the casings of the terminal devices. Plastic casings have excellent low dielectric properties, are easy to process, can be mass-produced, and are cost-effective, so they are increasingly being used in mid- to high-end terminal equipment.
On the other hand, plastic casings have the disadvantage that the surface is easily scratched and the appearance is inferior to glass or metal casings. For this reason, a method is used in which a coating is provided on the surface of the plastic casing.
Acrylic resins are often used in such coatings, and they develop excellent surface hardness (steel wool resistance) by being photocured by irradiation with actinic light.
As a coating layer for a plastic casing, Patent Documents 1 and 2 below propose a method of transferring a functional hard coat layer to satisfy scratch resistance. In Patent Documents 2 to 4, by using a silicon compound, steel wool resistance is obtained due to slipperiness, mold releasability, flexibility (flexibility), and stress relaxation.

特開２０１９－２５７３９号公報JP 2019-25739 Publication 特開２０１５－１９６７４８号公報Japanese Patent Application Publication No. 2015-196748 国際公開ＷＯ ２０１５／１５２２８８号International Publication WO 2015/152288 国際公開ＷＯ ２０１５／１５２２８９号International Publication WO 2015/152289

上記のような積層体では、コーティング層の耐スチールウール性を向上させることは常に求められる。一方、耐スチールウール性を向上させると耐屈曲性が低下し、携帯通信機器への使用時には筐体のコーティング層に変形やクラックが生じることがある。そこで、本発明は、スマートフォンなどの筐体用に使用した場合、耐スチールウール性、耐屈曲性を共に満足することができる筐体用コーティング膜およびそれを得るための光硬化性コーティング樹脂組成物を提供することを課題とする。 In the above-mentioned laminates, it is always required to improve the steel wool resistance of the coating layer. On the other hand, if the steel wool resistance is improved, the bending resistance is reduced, and when used in a mobile communication device, deformation or cracks may occur in the coating layer of the housing. Therefore, the present invention provides a coating film for a housing that satisfies both steel wool resistance and bending resistance when used for a housing such as a smartphone, and a photocurable coating resin composition for obtaining the coating film. The challenge is to provide the following.

すなわち本発明は、ポリメチルメタクリレートおよび／またはポリカーボネートからなる筐体上に形成されるコーティング膜であって、
当該コーティング膜の表面に対して、＃００００のスチールウールを１．５ｋｇ／ｃｍ２荷重で３００往復させた後に実質的に傷の発生が無く、かつ、
筐体上に膜厚みを１０μｍで形成し、当該コーティング膜を外側にして直径３０ｍｍの円筒に押し付け、屈曲角が１８０度となるように巻き付けた時、実質的に変形やクラックが認められないことを特徴とする筐体用コーティング膜、およびそれを得るための光硬化性コーティング樹脂組成物である。 That is, the present invention is a coating film formed on a casing made of polymethyl methacrylate and/or polycarbonate,
Substantially no scratches occur after #0000 steel wool is reciprocated 300 times at a load of 1.5 kg/ cm2 on the surface of the coating film, and
When a film with a thickness of 10 μm is formed on the casing and the coating film is pressed onto a cylinder with a diameter of 30 mm on the outside and wrapped so that the bending angle is 180 degrees, virtually no deformation or cracks are observed. A coating film for a housing characterized by the following, and a photocurable coating resin composition for obtaining the same.

本発明によれば、耐擦傷性と屈曲性を兼ね備えたコーティング膜を提供することができる。このような特性を備える本発明のコーティング膜は、特に、スマートフォンや携帯電話、通信機能付きのタブレット端末など携帯性に優れた端末機器の筐体に用いられる。 According to the present invention, a coating film having both scratch resistance and flexibility can be provided. The coating film of the present invention having such characteristics is particularly used for the casing of terminal devices with excellent portability, such as smartphones, mobile phones, and tablet terminals with communication functions.

以下、本発明を構成するそれぞれの要素について、詳細に説明するが、以下の説明は、本発明の実施の形態の一例であり、本発明はその要旨を超えない限り、以下の記載内容に限定されるものではない。なお、本明細書において「～」という表現を用いる場合、その前後の数値又は物性値を含む表現として用いるものとする。また、本発明において、「（メタ）アクリル」という表現を用いた場合、「アクリル」と「メタクリル」の一方又は両方を意味する。「（メタ）アクリレート」「（メタ）アクリロイル」についても同様である。 Each element constituting the present invention will be described in detail below, but the following explanation is an example of an embodiment of the present invention, and the present invention is limited to the following description unless it exceeds the gist thereof. It is not something that will be done. Note that when the expression "~" is used in this specification, it is used as an expression that includes numerical values or physical property values before and after it. Furthermore, in the present invention, when the expression "(meth)acrylic" is used, it means one or both of "acrylic" and "methacrylic". The same applies to "(meth)acrylate" and "(meth)acryloyl."

本発明の筐体用コーティング膜は、ポリメチルメタクリレートおよび／またはポリカーボネートからなる筐体（基材）上に形成されるコーティング膜であって、当該コーティング膜の表面に対して＃００００のスチールウールを１．５ｋｇ／ｃｍ２荷重で３００往復させた後に実質的に傷の発生が無く、かつ、筐体（基材）上に膜厚みを１０μｍで形成し、当該コーティング膜を外側にして直径３０ｍｍの円筒に押し付け、屈曲角が１８０度となるように巻き付けた時、実質的に変形やクラックが認められない。 The coating film for a housing of the present invention is a coating film formed on a housing (base material) made of polymethyl methacrylate and/or polycarbonate, and #0000 steel wool is applied to the surface of the coating film. After 300 reciprocations with a load of 1.5 kg/ cm2 , there is virtually no scratching, and a film with a thickness of 10 μm is formed on the casing (base material), and a diameter of 30 mm is formed with the coating film on the outside. When it is pressed against a cylinder and wrapped so that the bending angle is 180 degrees, virtually no deformation or cracks are observed.

このようなコーティング膜を与える光硬化性コーティング樹脂組成物（以下、単に、「組成物」等と記載する場合がある。）は、（a）光硬化性化合物、（b）光重合開始剤および（c）溶剤を含む。 A photocurable coating resin composition (hereinafter sometimes simply referred to as a "composition" etc.) that provides such a coating film contains (a) a photocurable compound, (b) a photoinitiator, and (c) Contains solvents.

（a）成分の光硬化性化合物は下記式（１）または（２）で表される光硬化性の多官能モノマーを必須の成分として含有する。

Figure 0007372805000001
Figure 0007372805000002
 （１）および（２）を含有することで硬化時の架橋密度が高くなり、結果、耐スチールウール性を満足することができる。上記（１）および（２）を含まない場合、硬化時の架橋密度が不足し、耐スチールウール性を満足することが困難である。 The photocurable compound of component (a) contains a photocurable polyfunctional monomer represented by the following formula (1) or (2) as an essential component.
Figure 0007372805000001
Figure 0007372805000002
 By containing (1) and (2), the crosslinking density during curing increases, and as a result, steel wool resistance can be satisfied. When the above-mentioned (1) and (2) are not included, the crosslinking density during curing is insufficient and it is difficult to satisfy steel wool resistance.

（a）成分の光硬化性化合物は１００ｇ当たりのアクリルモル数が０．８～１．１の範囲にある。アクリルモル数が０．８より小さい場合、架橋密度が低くなり耐擦傷性が低下する。反対に１．１より大きいと屈曲時にクラックを生じる。 The number of acrylic moles per 100 g of the photocurable compound (a) is in the range of 0.8 to 1.1. When the acrylic mole number is less than 0.8, the crosslinking density becomes low and the scratch resistance decreases. On the other hand, if it is larger than 1.1, cracks will occur during bending.

上記１００ｇ当たりのアクリルモル数とは、光硬化性化合物１００ｇ当たりの各成分のアクリルモル数（アクリル官能基数／分子量ｇ・mol-1）の総和を示す。 The number of acrylic moles per 100 g refers to the total number of acrylic moles (number of acrylic functional groups/molecular weight g·mol −1 ) of each component per 100 g of the photocurable compound.

（a）成分の光硬化性化合物は、７５質量％（ｗｔ％）以上が分子中に３個以上の（メタ）アクリル基を有する。７５ｗｔ％より少ないと架橋密度が低下し、耐スチールウール性を満足することが困難である。 75% by mass (wt%) or more of the photocurable compound as component (a) has three or more (meth)acrylic groups in the molecule. If it is less than 75 wt%, the crosslinking density will decrease and it will be difficult to satisfy the steel wool resistance.

分子中に３個以上の（メタ）アクリル基を有する化合物としてはペンタエリスリトールトリアクリレート、ペンタエリスリトールテトラアクリレート、ジペンタエリスリトールヘキサアクリレート、トリメチロールプロパントリアクリレート、ジメチロールプロパンテトラアクリレート、トリメチロールプロパンエチレンオキシド変性トリアクリレートトリメチロールプロパンプロピレンオキシド変性トリアクリレート、ペンタエリスリトールエチレンオキシド変性テトラアクリレート、ジペンタエリスリトールエチレンオキシド変性ペンタアクリレート、ジペンタエリスリトールエチレンオキシド変性ヘキサアクリレート、トリス（２－アクリロイルオキシエチル）イソシアヌレートが挙げられる。 Examples of compounds having three or more (meth)acrylic groups in the molecule include pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, trimethylolpropane triacrylate, dimethylolpropane tetraacrylate, and trimethylolpropane modified with ethylene oxide. Triacrylate trimethylol propane propylene oxide modified triacrylate, pentaerythritol ethylene oxide modified tetraacrylate, dipentaerythritol ethylene oxide modified pentaacrylate, dipentaerythritol ethylene oxide modified hexaacrylate, tris (2-acryloyloxyethyl) isocyanurate.

（a）成分の光硬化性化合物は１００ｇ当たりの水酸基のモル数が０．０６～０．２０の範囲にある。この範囲に満たないと弾性率が低下し、所望する耐スチールウール性が得られない。反対にこの範囲を超えて含有しても更なる向上は望めない。 The number of moles of hydroxyl groups per 100 g of the photocurable compound (a) is in the range of 0.06 to 0.20. If it is less than this range, the elastic modulus decreases and the desired steel wool resistance cannot be obtained. On the other hand, if the content exceeds this range, no further improvement can be expected.

上記１００ｇ当たりの水酸基のモル数とは、光硬化性化合物１００ｇ当たりの各成分の水酸基モル数（水酸基数／分子量ｇ・mol-1）の総和を示す。 The above-mentioned number of moles of hydroxyl groups per 100 g indicates the sum of the number of moles of hydroxyl groups of each component per 100 g of the photocurable compound (number of hydroxyl groups/molecular weight g·mol −1 ).

水酸基含有（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、２－ヒドロキシブチル（メタ）アクリレート、２－ヒドロキシ－３－フェノキシプロピル（メタ）アクリレート、２－（メタ）アクリロイロキシエチル－２－ヒドロキシエチル-フタル酸、グリセリンジ（メタ）アクリレート、２－ヒドロキシ－３－（メタ）アクリロイロキシプロピル（メタ）アクリレート、ペンタエリスリトールトリアクリレート、ジペンタエリスリトールペンタアクリレートなどが挙げられる。中でも３官能以上のものが好ましい。 Examples of hydroxyl group-containing (meth)acrylates include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, and 2-hydroxypropyl (meth)acrylate. (meth)acryloyloxyethyl-2-hydroxyethyl-phthalic acid, glycerin di(meth)acrylate, 2-hydroxy-3-(meth)acryloyloxypropyl (meth)acrylate, pentaerythritol triacrylate, dipentaerythritol penta Examples include acrylate. Among them, those having trifunctionality or more are preferable.

（a）成分の光硬化性化合物については、１００ｇ当たりのアクリルモル数および水酸基のモル数を調整するため、分子内に２個以下のアクリレートを含むことができる。 Regarding the photocurable compound of component (a), two or less acrylates can be included in the molecule in order to adjust the number of acrylic moles and the number of moles of hydroxyl groups per 100 g.

上記分子内に２個以下のアクリレートを含む化合物の具体例としては、１，４－ブタンジオールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、１，９－ノナンジオールジ（メタ）アクリレート、テトラエチレングリコール時メタクリレート、ジシクロペンタニルジメチロールジ（メタ）アクリレート等が挙げられる。 Specific examples of the compounds containing two or less acrylates in the molecule include 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and 1,9-nonanediol di(meth)acrylate. Examples include meth)acrylate, tetraethylene glycol methacrylate, dicyclopentanyldimethyloldi(meth)acrylate, and the like.

また、（a）成分の光硬化性化合物はウレタン変性（メタ）アクリレート類やエチレンオキサイド変性（メタ）アクリレート類を含んでもよい。これらは筐体用コーティング膜の屈曲性を改善するのに有効である。 Further, the photocurable compound of component (a) may include urethane-modified (meth)acrylates or ethylene oxide-modified (meth)acrylates. These are effective in improving the flexibility of the coating film for the housing.

光硬化性コーティング樹脂組成物の（b）光重合開始剤としては、例えばベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインプロピルエーテル、ベンゾインイソブチルエーテル等のベンゾイン類；アセトフェノン、２，２－ジエトキシ－２－フェニルアセトフェノン、２，２－ジエトキシ－２－フェニルアセトフェノン、１，１－ジクロロアセトフェノン、２－ヒドロキシ－２－メチル－フェニルプロパン－１－オン、ジエトキシアセトフェノン、１－ヒドロキシシクロヘキシルフェニルケトン、２－メチル－１－〔４－（メチルチオ）フェニル〕－２－モルホリノプロパン－１－オンなどのアセトフェノン類；２－エチルアントラキノン、２－ターシャリーブチルアントラキノン、２－クロロアントラキノン、２－アミルアントラキノンなどのアントラキノン類；２，４－ジエチルチオキサントン、２－イソプロピルチオキサントン、２－クロロチオキサントンなどのチオキサントン類；アセトフエノンジメチルケタール、ベンジルジメチルケタールなどのケタール類；ベンゾフェノン、４－ベンゾイル－４'－メチルジフェニルサルファイド、４，４'－ビスメチルアミノベンゾフェノンなどのベンゾフェノン類；２，４，６－トリメチルベンゾイルジフェニルホスフィンオキサイド、ビス（２，４，６－トリメチルベンゾイル）－フェニルホスフィンオキサイド等のホスフィンオキサイド類等が挙げられる。 Examples of the photopolymerization initiator (b) of the photocurable coating resin composition include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether; acetophenone, 2,2-diethoxy-2 -phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, 2- Acetophenones such as methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one; anthraquinones such as 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-chloroanthraquinone, and 2-amylanthraquinone; Thioxanthones such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone, and 2-chlorothioxanthone; Ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, Benzophenones such as 4,4'-bismethylaminobenzophenone; phosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, etc. .

これらは、単独又は２種以上の混合物として使用でき、更にはトリエタノールアミン、メチルジエタノールアミンなどの第３級アミン、Ｎ，Ｎ－ジメチルアミノ安息香酸エチルエステル、Ｎ，Ｎ－ジメチルアミノ安息香酸イソアミルエステル等の安息香酸誘導体等の促進剤などと組み合わせて使用することができる。 These can be used alone or as a mixture of two or more, and further include tertiary amines such as triethanolamine and methyldiethanolamine, N,N-dimethylaminobenzoic acid ethyl ester, and N,N-dimethylaminobenzoic acid isoamyl ester. It can be used in combination with accelerators such as benzoic acid derivatives.

（ｂ）成分の光重合開始剤は、（ａ）成分の合計１００ｗｔ％に対し０．１～２０ｗｔ％、好ましくは１～１０ｗｔ％である。この範囲に満たないと架橋が不十分になって弾性率が低下し、所望する耐スチールウール性が得られない。反対にこの範囲を超えて含有しても更なる反応率の向上は望めない。 The amount of the photopolymerization initiator as component (b) is 0.1 to 20 wt%, preferably 1 to 10 wt%, based on the total 100 wt% of component (a). If it is less than this range, crosslinking becomes insufficient and the elastic modulus decreases, making it impossible to obtain the desired steel wool resistance. On the other hand, if the content exceeds this range, no further improvement in the reaction rate can be expected.

（ｃ）成分の溶剤としては、トルエン、キシレン等の芳香族系有機溶剤、メチルエチルケトン、メチルイソブチルケトン等のケトン系有機溶剤、酢酸エチル、酢酸ｎ－プロピル、酢酸イソプロピル、酢酸イソブチル等のエステル系有機溶剤、メタノール、エタノール、ｎ－プロパノール、イソプロパノール、ｎ－ブタノール等のアルコール系有機溶剤プロピレングリコールモノメチルエーテル等のグリコールエーテル系有機溶剤など公知の有機溶剤を使用できる。特にグリコール系有機溶剤を含むことが好ましい。 The solvent for component (c) includes aromatic organic solvents such as toluene and xylene, ketone organic solvents such as methyl ethyl ketone and methyl isobutyl ketone, and ester organic solvents such as ethyl acetate, n-propyl acetate, isopropyl acetate, and isobutyl acetate. Known organic solvents can be used, such as alcohol-based organic solvents such as methanol, ethanol, n-propanol, isopropanol, and n-butanol, and glycol ether-based organic solvents such as propylene glycol monomethyl ether. In particular, it is preferable to include a glycol-based organic solvent.

上記グリコールエーテル系有機溶剤としては、例えばエチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、エチレングリコールｎ－プロピルエーテル、エチレングリコールモノイソプロピルエーテル、エチレングリコールジプロピルエーテル、エチレングリコールモノブチルエーテル、エチレングリコールモノイソブチルエーテル、エチレングリコールジブチルエーテル、エチレングリコールイソアミルエーテル、エチレングリコールモノヘキシルエーテル、エチレングリコールモノ２－エチルヘキシルエーテル、メトキシエトキシエタノール、エチレングリコールモノアリルエーテル等のエチレングリコールエーテル類、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノプロピルエーテル、プロピレングリコールモノブチルエーテル、ブトキシプロパノール等のプロピレングリコール類が挙げられ、中でもプロピレングリコールモノメチルエーテルが好ましい。 Examples of the glycol ether organic solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol n-propyl ether, ethylene glycol monoisopropyl ether, ethylene glycol dipropyl ether, and ethylene glycol dipropyl ether. Ethylene glycol ethers such as glycol monobutyl ether, ethylene glycol monoisobutyl ether, ethylene glycol dibutyl ether, ethylene glycol isoamyl ether, ethylene glycol monohexyl ether, ethylene glycol mono 2-ethylhexyl ether, methoxyethoxyethanol, ethylene glycol monoallyl ether, Examples include propylene glycols such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, and butoxypropanol, among which propylene glycol monomethyl ether is preferred.

本発明の筐体用光硬化性コーティング樹脂組成物には、本発明の目的から外れない範囲で各種添加剤を添加することができる。各種添加剤として有機／無機フィラー、スリップ剤、可塑剤、難燃剤、熱安定剤、酸化防止剤、光安定剤、紫外線吸収剤、滑剤、帯電防止剤、離型剤、発泡剤、核剤、着色剤、架橋剤、分散助剤、樹脂成分等を例示することができる。 Various additives can be added to the photocurable coating resin composition for a housing of the present invention as long as they do not depart from the purpose of the present invention. Various additives include organic/inorganic fillers, slip agents, plasticizers, flame retardants, heat stabilizers, antioxidants, light stabilizers, ultraviolet absorbers, lubricants, antistatic agents, mold release agents, foaming agents, nucleating agents, Examples include colorants, crosslinking agents, dispersion aids, and resin components.

本発明の筐体用光硬化性コーティング樹脂組成物は、波長１０～４００ｎｍの紫外線や波長４００～７００ｎｍの可視光線を照射することで、硬化することができる。用いる光の波長は特に制限されるものではないが、特に波長２００～４００ｎｍの近紫外線が好適に用いられる。紫外線発生源として用いられるランプとしては、低圧水銀ランプ（出力：０．４～４Ｗ／ｃｍ）、高圧水銀ランプ（４０～１６０Ｗ／ｃｍ）、超高圧水銀ランプ（１７３～４３５Ｗ／ｃｍ）、メタルハライドランプ（８０～１６０Ｗ／ｃｍ）等を例示することができる。 The photocurable coating resin composition for a housing of the present invention can be cured by irradiation with ultraviolet rays with a wavelength of 10 to 400 nm or visible light with a wavelength of 400 to 700 nm. Although the wavelength of the light used is not particularly limited, near ultraviolet light with a wavelength of 200 to 400 nm is particularly preferably used. Lamps used as ultraviolet light sources include low-pressure mercury lamps (output: 0.4 to 4 W/cm), high-pressure mercury lamps (40 to 160 W/cm), ultra-high pressure mercury lamps (173 to 435 W/cm), and metal halide lamps. (80 to 160 W/cm).

光照射によってコーティング膜を得る方法としては、酸素遮断雰囲気下あるいは大気雰囲気下のどちらであってもよいが、本発明の組成物は大気雰囲気下での重合硬化であっても、良好なコーティングを与える。例えば流涎法、ローラーコート法、バーコート法、スプレーコート法、エアーナイフコート法、スピンコート法、フローコート法、カーテンコート法およびディッピング法が挙げられる。なお、塗工膜厚については。乾燥と硬化後の成形膜厚を考慮して、固形分濃度により調整する。 The method for obtaining a coating film by light irradiation may be either in an oxygen-blocking atmosphere or in an air atmosphere, but the composition of the present invention can form a good coating even when polymerized and cured in an air atmosphere. give. Examples include drooling method, roller coating method, bar coating method, spray coating method, air knife coating method, spin coating method, flow coating method, curtain coating method and dipping method. Regarding the coating film thickness. The solid content concentration is adjusted in consideration of the thickness of the formed film after drying and curing.

本発明の筐体に使用される素材としては、ポリメチルメタクリレートおよび／またはポリカーボネートが使用される。これらの素材を平板状または１面が解放された箱状に成形された状態で光硬化性コーティング樹脂組成物が塗工される。筐体の厚さとしては、軽量化のためできるだけ薄いことが好ましいが、一定の強度を保つために、筐体の厚さは好ましくは０．１～２ｍｍの範囲、より好ましくは０．１～１ｍｍの範囲でである。 The material used for the casing of the present invention is polymethyl methacrylate and/or polycarbonate. A photocurable coating resin composition is applied to these materials in the form of a flat plate or a box with one side open. The thickness of the casing is preferably as thin as possible to reduce weight, but in order to maintain a certain level of strength, the thickness of the casing is preferably in the range of 0.1 to 2 mm, more preferably 0.1 to 2 mm. This is within a range of 1 mm.

以下、実施例及び比較例に基づいて本発明を具体的に説明するが、本発明は以下の実施例に限定されるものではない。 Hereinafter, the present invention will be specifically explained based on Examples and Comparative Examples, but the present invention is not limited to the following Examples.

（製造例１）＜筐体用光硬化性コーティング樹脂組成物Ａ１の作製＞
ジペンタエリスリトールヘキサアクリレート：Ｍｗ＝５７８．５７、アクリル基数＝６、水酸基数＝０〔内ジペンタエリスリトールペンタアクリレート（Ｍｗ＝５２４．５２、アクリル基数＝５、水酸基数＝１）を３５％含む〕（共栄社化学社製 製品名ＤＰＨＡ）６０重量部、ペンタエリスリトールトリアクリレート：Ｍｗ＝２９８．２９、アクリル基数＝３、水酸基数＝１〔内ペンタエリスリトールテトラアクリレート（Ｍｗ＝３５２．３４、アクリル基数＝４、水酸基数＝０）を４０％含む〕（共栄社化学社製 ライトアクリレートＰＥ－３Ａ）２０重量部、トリメチロールプロパントリアクリレート：Ｍｗ＝２９６．３２、アクリル基数＝３、水酸基数＝０（共栄社化学社製 ライトアクリレートＴＭＰ－Ａ）２０重量部を混合し、さらに光重合開始剤として２－メチル－１－[４－（メチルチオ）フェニル]－２－モルフォリノプロパン－１－オン（ＩＧＭ Ｒｅｓｉｎｓ Ｂ．Ｖ．社製 Ｏｍｎｉｒａｄ ９０７）８重量部、有機溶剤としてプロピレングリコールモノメチルエーテルを固形分４０％となるように調整して、筐体用コーティング樹脂組成物Ａ１を得た。この光硬化性樹脂のアクリルモル数は｛［（６／５７８．５７×０．６５）＋（５／５２４．５２×０．３５）］×０．６＋［（４／３５２．３４×０．４）＋（３／２９８．２９×０．６）］×０．２＋（３／２９６．３２）×０．２｝×１００＝１．０２、水酸基のモル数は［（１／５２４．５２×０．３５）×０．６＋（１／２９８．２９×０．６）×０．２］×１００＝０．０８、３官能以上の比率は１００％であった。 (Production Example 1) <Preparation of photocurable coating resin composition A1 for housing>
Dipentaerythritol hexaacrylate: Mw = 578.57, number of acrylic groups = 6, number of hydroxyl groups = 0 [Contains 35% dipentaerythritol pentaacrylate (Mw = 524.52, number of acrylic groups = 5, number of hydroxyl groups = 1)] (manufactured by Kyoeisha Chemical Co., Ltd., product name DPHA) 60 parts by weight, pentaerythritol triacrylate: Mw = 298.29, number of acrylic groups = 3, number of hydroxyl groups = 1 [incl. pentaerythritol tetraacrylate (Mw = 352.34, number of acrylic groups = 4) , number of hydroxyl groups = 0)] (light acrylate PE-3A manufactured by Kyoeisha Chemical Co., Ltd.) 20 parts by weight, trimethylolpropane triacrylate: Mw = 296.32, number of acrylic groups = 3, number of hydroxyl groups = 0 (Kyoeisha Chemical Co., Ltd.) 20 parts by weight of light acrylate TMP-A) manufactured by IGM Resins B. Co., Ltd. were mixed, and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (IGM Resins B. 8 parts by weight of Omnirad 907 (manufactured by V. Co., Ltd.) and propylene glycol monomethyl ether as an organic solvent were adjusted to a solid content of 40% to obtain a coating resin composition A1 for a housing. The number of acrylic moles of this photocurable resin is {[(6/578.57×0.65)+(5/524.52×0.35)]×0.6+[(4/352.34×0. 4)+(3/298.29×0.6)]×0.2+(3/296.32)×0.2}×100=1.02, the number of moles of hydroxyl group is [(1/524.52 x 0.35) x 0.6 + (1/298.29 x 0.6) x 0.2] x 100 = 0.08, and the ratio of trifunctional or higher functions was 100%.

（実施例１）＜ポリメチルメタクリレート／ポリカーボネート積層基材へのコーティング被膜の作製＞
筐体用光硬化性コーティング樹脂組成物Ａ１をポリメチルメタクリレート／ポリカーボネート積層基材（厚み６５０μｍ、長さ１０ｃｍ、幅１０ｃｍ エスカーボシート社製）上、ポリメチルメタクリレート側にスピンコート法により乾燥後の膜厚が１０μｍになるように塗布し、８０℃で５分乾燥した後、室温下５分冷却した。その後、酸素雰囲気下、２ｋＷ／ｃｍ２の高圧水銀ランプを用い、２，８００ｍＪ／ｃｍ２積算露光量（３６５ｎｍ換算）で製膜し、筐体用積層体Ｓ１を得た。 (Example 1) <Preparation of coating film on polymethyl methacrylate/polycarbonate laminated base material>
After drying, the photocurable coating resin composition A1 for the housing was spin-coated on the polymethyl methacrylate side on a polymethyl methacrylate/polycarbonate laminated base material (thickness 650 μm, length 10 cm, width 10 cm, manufactured by Escarbosheet Co., Ltd.). It was coated to a film thickness of 10 μm, dried at 80° C. for 5 minutes, and then cooled to room temperature for 5 minutes. Thereafter, a film was formed in an oxygen atmosphere using a 2 kW/cm 2 high-pressure mercury lamp at a cumulative exposure dose of 2,800 mJ/cm 2 (365 nm equivalent) to obtain a casing laminate S1.

（実施例５）＜ポリカーボネート基材へのコーティング被膜の作製＞
筐体用光硬化性コーティング樹脂組成物Ａ１をポリカーボネート基材（厚み５００μｍ、長さ１０ｃｍ、幅１０ｃｍ 旭硝子社製）上にスピンコート法により乾燥後の膜厚が１０μｍになるように塗布し、８０℃で５分乾燥した後、室温下５分冷却した。その後、酸素雰囲気下、２ｋＷ／ｃｍ２の高圧水銀ランプを用い、２，８００ｍＪ／ｃｍ２積算露光量（３６５ｎｍ換算）で製膜し筐体用積層体Ｔ１を得た。 (Example 5) <Preparation of coating film on polycarbonate base material>
The photocurable coating resin composition A1 for the housing was applied onto a polycarbonate base material (thickness 500 μm, length 10 cm, width 10 cm, manufactured by Asahi Glass Co., Ltd.) by a spin coating method so that the film thickness after drying was 10 μm. After drying at ℃ for 5 minutes, it was cooled to room temperature for 5 minutes. Thereafter, a film was formed in an oxygen atmosphere using a 2 kW/cm 2 high-pressure mercury lamp at a cumulative exposure dose of 2,800 mJ/cm 2 (365 nm equivalent) to obtain a casing laminate T1.

（製造例２～８）
表１に記載の原料および組成比率を用いた以外は製造例１と同様の手順で筐体用光硬化性コーティング樹脂組成物Ａ２～Ａ４（製造例２～４）およびＢ１～Ｂ４（製造例５～８）を得た。
なお、表中の略称は以下を示す。
ＰＥ－４Ａ：ペンタエリスリトールテトラアクリレート：Ｍｗ＝３５２．３４アクリル基数＝４（共栄社化学社製）
ＤＣＰＡ：ジメチロール－トリシクロデカンジアクリレート：Ｍｗ＝３０４．３９ アクリル基数＝２（共栄社化学社製）
Ｇ２０１Ｐ：２－ヒドロキシ－３－アクリロイロキシプロピルメタクリレート：Ｍｗ＝２１４．２２ （メタ）アクリル基数＝２ 水酸基数＝１（共栄社化学社製）
ＴＭＰ－６ＥＯ－３Ａ：６ＥＯ変性トリメチロールプロパントリアクリレート：Ｍｗ＝５６０．６４ アクリル基数＝３（共栄社化学社製）
ＥＢＥＣＲＹＬ２１０：芳香族ウレタンアクリレート：Ｍｗ＝１５００、アクリル基数＝２（ダイセル・オルネクス社製）
光硬化性樹脂１００ｇ当たりのアクリルモル数＝光硬化性樹脂１００ｇ当たりの各成分のアクリルモル数（アクリル官能基数／分子量ｇ・mol-1）の総和
光硬化性樹脂１００ｇ当たりの水酸基モル数＝光硬化性樹脂１００ｇ当たりの各成分の水酸基数（水酸基数／分子量ｇ・mol-1）の総和 (Manufacturing examples 2 to 8)
Photocurable coating resin compositions A2 to A4 (Production Examples 2 to 4) and B1 to B4 (Production Examples 5 ~8) was obtained.
The abbreviations in the table are as follows.
PE-4A: Pentaerythritol tetraacrylate: Mw = 352.34 Acrylic group number = 4 (manufactured by Kyoeisha Chemical Co., Ltd.)
DCPA: Dimethylol-tricyclodecane diacrylate: Mw = 304.39 Number of acrylic groups = 2 (manufactured by Kyoeisha Chemical Co., Ltd.)
G201P: 2-Hydroxy-3-acryloyloxypropyl methacrylate: Mw = 214.22 Number of (meth)acrylic groups = 2 Number of hydroxyl groups = 1 (manufactured by Kyoeisha Chemical Co., Ltd.)
TMP-6EO-3A: 6EO modified trimethylolpropane triacrylate: Mw = 560.64 Number of acrylic groups = 3 (manufactured by Kyoeisha Chemical Co., Ltd.)
EBECRYL210: Aromatic urethane acrylate: Mw = 1500, number of acrylic groups = 2 (manufactured by Daicel Allnex)
Number of acrylic moles per 100 g of photocurable resin = Total number of acrylic moles of each component (number of acrylic functional groups/molecular weight g mol -1 ) per 100 g of photocurable resin Number of moles of hydroxyl groups per 100 g of photocurable resin = light Total number of hydroxyl groups (number of hydroxyl groups/molecular weight g・mol -1 ) of each component per 100 g of curable resin

(実施例２～４、実施例６～８)
＜積層体Ｓ２～Ｓ４、Ｔ２～Ｔ４の作製＞
表１の組成比率で配合された筐体用光硬化性コーティング樹脂組成物Ａ２～Ａ４を用いたこと以外は実施例１と同じ手順で筐体用積層体Ｓ２～Ｓ４（実施例２～４）を作製し、また、実施例５と同じ手順でＴ２～Ｔ４（実施例６～８）を作製した。 (Examples 2-4, Examples 6-8)
<Production of laminates S2 to S4 and T2 to T4>
Laminated bodies S2 to S4 for housings (Examples 2 to 4) were prepared in the same manner as in Example 1 except that photocurable coating resin compositions A2 to A4 for housings were used in the composition ratios shown in Table 1. In addition, T2 to T4 (Examples 6 to 8) were manufactured using the same procedure as in Example 5.

(比較例１～８)
＜積層体Ｕ１～Ｕ４、Ｖ１～Ｖ４の作製＞
表１の組成比率で配合された筐体用光硬化性コーティング樹脂組成物Ｂ１～Ｂ４を用いたこと以外は上記と同じ手順で筐体用積層体Ｕ１～Ｕ４（比較例１～４）、Ｖ１～Ｖ４（比較例５～８）を作製した。 (Comparative Examples 1 to 8)
<Production of laminates U1 to U4, V1 to V4>
Laminated bodies U1 to U4 (Comparative Examples 1 to 4) and V1 ~V4 (Comparative Examples 5 to 8) were produced.

＜評価＞
上記にて得られた筐体用積層体Ｓ１～Ｓ４およびＴ１～Ｔ４（実施例）、並びに筐体用積層体Ｕ１～Ｕ４およびＶ１～Ｖ４（比較例）を用いて、以下の評価を行った。なお評価結果を表２および表３に示した。 <Evaluation>
The following evaluations were performed using the laminates for housings S1 to S4 and T1 to T4 (examples) and the laminates for housings U1 to U4 and V1 to V4 (comparative examples) obtained above. . The evaluation results are shown in Tables 2 and 3.

＜耐スチールウール性＞
筐体用積層体Ｓ１～Ｓ４およびＴ１～Ｔ４（実施例）、並びに筐体用積層体Ｕ１～Ｕ４およびＶ１～Ｖ４（比較例）を用いて、それぞれを♯００００のスチールウールを用い、往復摩耗試験機（Ｔｙｐｅ：３０Ｓ ＨＥＩＤＯＮ社製）を用いて、荷重１．５ｋｇ／ｃｍ２にてコーティング膜の表面を３００往復摩耗した。傷の発生の有無を目視により観察し、以下の基準にのっとり判定を行い、７点以上を○とした。
１０点：０本
７点：１本以上、５本未満
４点：５本以上、１０本未満
１点：１０本以上 <Steel wool resistance>
Using the case laminates S1 to S4 and T1 to T4 (examples) and the case laminates U1 to U4 and V1 to V4 (comparative examples), each was subjected to reciprocating abrasion using #0000 steel wool. Using a testing machine (Type: 30S manufactured by HEIDON), the surface of the coating film was abraded 300 times back and forth under a load of 1.5 kg/cm 2 . The presence or absence of scratches was visually observed and judged according to the following criteria, and scores of 7 or more were rated as ○.
10 points: 0 lines 7 points: 1 or more, less than 5 lines 4 points: 5 or more, less than 10 lines 1 point: 10 lines or more

＜耐屈曲性＞
筐体用積層体Ｓ１～Ｓ４およびＴ１～Ｔ４（実施例）、並びに積層体Ｕ１～Ｕ４およびＶ１～Ｖ４（比較例）を８０×５０ｍｍ角にカットして試験材とし、それぞれ、コーティング膜面を外側にして、直径３０ｍｍのアクリル製の円筒に対して、試験材（基材面側）の長い辺が円筒の円周に沿うように屈曲角が１８０度（Ｕ字状）となるまで巻き付け、コーティング膜の変形やクラックを目視にて観察した。
○：変形やクラックが発生しない
×：変形やクラックが発生する <Bending resistance>
The laminates S1 to S4 and T1 to T4 (examples) and the laminates U1 to U4 and V1 to V4 (comparative examples) for housings were cut into 80 x 50 mm squares to be used as test materials, and the coating film surface was Wrap the test material (on the base material side) around an acrylic cylinder with a diameter of 30 mm on the outside so that the long side follows the circumference of the cylinder until the bending angle is 180 degrees (U-shape). Deformation and cracks in the coating film were visually observed.
○: No deformation or cracks occur ×: Deformation or cracks occur

Figure 0007372805000003
Figure 0007372805000003

Figure 0007372805000004
Figure 0007372805000004

Figure 0007372805000005
Figure 0007372805000005

Claims (4)

ポリメチルメタクリレートおよび／またはポリカーボネートからなる筐体上に形成されるコーティング膜であって、
当該コーティング膜は、(a）光硬化性化合物、（b）光重合開始剤および（c）溶剤を含む筐体用光硬化性コーティング樹脂組成物の硬化物であって、(a）光硬化性化合物が下記式（１）で表される光硬化性多官能モノマー及び下記式（２）で表される光硬化性多官能モノマーを必須の成分として含有すると共に該光硬化性化合物の１００ｇ当たりの水酸基のモル数が０．０６以上０．２以下であり、
当該コーティング膜の表面に対して、＃００００のスチールウールを１．５ｋｇ／ｃｍ２荷重で３００往復させた後に傷の発生が５本未満であり、かつ、
筐体上に膜厚みを１０μｍで形成し、当該コーティング膜を外側にして直径３０ｍｍの円筒に押し付け、屈曲角が１８０度となるように巻き付けた時、変形やクラックが発生しないことを特徴とする筐体用コーティング膜（但し、エポキシ基を有する化合物の硬化物を含む場合を除く）。
Figure 0007372805000006
Figure 0007372805000007
 A coating film formed on a casing made of polymethyl methacrylate and/or polycarbonate,
The coating film is a cured product of a photocurable coating resin composition for a housing containing (a) a photocurable compound, (b) a photopolymerization initiator, and (c) a solvent. The compound contains a photocurable polyfunctional monomer represented by the following formula (1) and a photocurable polyfunctional monomer represented by the following formula (2) as essential components, and the The number of moles of hydroxyl groups is 0.06 or more and 0.2 or less,
Less than 5 scratches occur after #0000 steel wool is reciprocated 300 times at a load of 1.5 kg/cm 2 on the surface of the coating film, and
A film with a thickness of 10 μm is formed on the casing, and when the coating film is pressed onto a cylinder with a diameter of 30 mm on the outside and wrapped so that the bending angle is 180 degrees , no deformation or cracks occur. Coating film for the housing (excluding cases containing a cured product of a compound having an epoxy group).
Figure 0007372805000006
Figure 0007372805000007
 ポリメチルメタクリレートおよび／またはポリカーボネートからなる筐体上に形成され、以下の（ｉ）及び（ｉｉ）を満足する筐体用のコーティング膜を得るための光硬化性コーティング樹脂組成物であって、(a）光硬化性化合物、（b）光重合開始剤および（c）溶剤を含み、(a）光硬化性化合物が下記式（１）で表される光硬化性多官能モノマー及び下記式（２）で表される光硬化性多官能モノマーを必須の成分として含有すると共に該光硬化性化合物の１００ｇ当たりの水酸基のモル数が０．０６以上０．２以下であることを特徴とする筐体用光硬化性コーティング樹脂組成物（但し、当該筐体用のコーティング膜として、エポキシ基を有する化合物の硬化物を含む場合を除く）。
(i)当該コーティング膜の表面に対して、＃００００のスチールウールを１．５ｋｇ／ｃｍ２荷重で３００往復させた後に傷の発生が５本未満であること。
(ii)筐体上に膜厚みを１０μｍで形成し、当該コーティング膜を外側にして直径３０ｍｍの円筒に押し付け、屈曲角が１８０度となるように巻き付けた時、変形やクラックが発生しないこと。
Figure 0007372805000008
Figure 0007372805000009
 A photocurable coating resin composition for obtaining a coating film for a housing that is formed on a housing made of polymethyl methacrylate and/or polycarbonate and satisfies the following (i) and (ii), A photocurable polyfunctional monomer containing a) a photocurable compound, (b) a photopolymerization initiator, and (c) a solvent, in which the photocurable compound is represented by the following formula (1) and the following formula (2). ) as an essential component, and the number of moles of hydroxyl groups per 100 g of the photocurable compound is 0.06 or more and 0.2 or less. photocurable coating resin composition for use in the housing (excluding cases in which the coating film for the housing contains a cured product of a compound having an epoxy group).
(i) Less than 5 scratches occur after #0000 steel wool is reciprocated 300 times at a load of 1.5 kg/ cm2 on the surface of the coating film.
(ii) When a film with a thickness of 10 μm is formed on the casing and the coating film is pressed onto a cylinder with a diameter of 30 mm on the outside and wrapped so that the bending angle is 180 degrees , no deformation or cracks will occur. .
Figure 0007372805000008
Figure 0007372805000009
 光硬化性化合物の１００ｇ当たりのアクリルモル数が０．８以上、１．１未満であることを特徴とする請求項２に記載の筐体用光硬化性コーティング樹脂組成物。 The photocurable coating resin composition for a housing according to claim 2, wherein the number of acrylic moles per 100 g of the photocurable compound is 0.8 or more and less than 1.1. 光硬化性化合物の７５ｗｔ％以上が分子中に３個以上の（メタ）アクリル基を有することを特徴とする請求項２に記載の筐体用光硬化性コーティング樹脂組成物。 3. The photocurable coating resin composition for a housing according to claim 2, wherein 75 wt% or more of the photocurable compound has three or more (meth)acrylic groups in the molecule.
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