JP2002128815A - Photocurable composition and its curing method - Google Patents

Photocurable composition and its curing method

Info

Publication number
JP2002128815A
JP2002128815A JP2000321110A JP2000321110A JP2002128815A JP 2002128815 A JP2002128815 A JP 2002128815A JP 2000321110 A JP2000321110 A JP 2000321110A JP 2000321110 A JP2000321110 A JP 2000321110A JP 2002128815 A JP2002128815 A JP 2002128815A
Authority
JP
Japan
Prior art keywords
photocurable composition
surfactant
emulsion
variable
photocurable
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
JP2000321110A
Other languages
Japanese (ja)
Inventor
Shigenori Nagahara
重徳 永原
Naohiro Honda
直弘 本田
Satoshi Imahashi
聰 今橋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toyobo Co Ltd
Original Assignee
Toyobo Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toyobo Co Ltd filed Critical Toyobo Co Ltd
Priority to JP2000321110A priority Critical patent/JP2002128815A/en
Priority to TW090124936A priority patent/TW539921B/en
Priority to CN01136436XA priority patent/CN1216950C/en
Priority to KR1020010064607A priority patent/KR20020031072A/en
Publication of JP2002128815A publication Critical patent/JP2002128815A/en
Pending legal-status Critical Current

Links

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active 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
    • 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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/285—Permanent coating compositions
    • H05K3/287—Photosensitive compositions

Abstract

PROBLEM TO BE SOLVED: To obtain a photocurable emulsion composition and a method of curing it which solve problems of a conventional photocurable composition, such as VOC, productivity and labor cost, or those of a cured article consisting of a conventional photocurable emulsion composition, such as water resistance (resistance to boiling water), acid resistance, solvent resistance and a photosensitive characteristic. SOLUTION: This photocurable composition contains a reactive monomer and/or a reactive prepolymer, a photoinitiator, emulsion particles and a variable surfactant as an emulsifier. The method of curing the photocurable composition is characterized in that a heat treatment and/or an active energy beam irradiation treatment is implemented after coating with the photocurable composition.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【発明の属する技術分野】本発明は、光硬化性組成物に
関する。更に詳しくは、光硬化性組成物に可変性界面活
性剤を含有することによって、熱および／または活性エ
ネルギー線照射処理によって可変性界面活性剤が、例え
ば熱分解および／または光分解反応し、得られた硬化物
が耐水性（耐沸水性）、耐酸性、耐溶剤性、感光特性等
に優れた特性を示し、各種用途、例えば、塗料、印刷イ
ンキ、表面コート剤、フォトレジストインキ、接着剤等
の用途に適した光硬化性組成物およびその硬化方法に関
する。[0001] The present invention relates to a photocurable composition. More specifically, by including a variable surfactant in the photocurable composition, the variable surfactant can be subjected to, for example, a thermal decomposition and / or a photolysis reaction by heat and / or active energy ray irradiation treatment to obtain the variable surfactant. The cured product shows excellent properties such as water resistance (boiling water resistance), acid resistance, solvent resistance, and photosensitivity, and is used in various applications, such as paints, printing inks, surface coating agents, photoresist inks, and adhesives. The present invention relates to a photocurable composition suitable for applications such as, and a curing method thereof.

【０００２】[0002]

【従来の技術】従来より光硬化性組成物は、臭気、毒
性、大気汚染等のＶＯＣ（揮発性有機溶剤）問題、生産
性や設備の簡素化による省エネルギー化、労務コストの
削減による省力化等の課題を解決する目的で幅広い分野
で使用されている。しかしながら光硬化性組成物の特徴
である速硬化性や塗工性をより良くするために比較的低
分子量の反応性モノマーや有機溶剤を併用する場合が多
く、これらの有機溶剤や反応性モノマーの有毒性、臭
気、引火性、刺激性等が問題である。2. Description of the Related Art Conventionally, photocurable compositions have been known to have problems of volatile organic solvents (VOC) such as odor, toxicity, air pollution, etc., energy saving by simplifying productivity and equipment, and labor saving by reducing labor costs. Is used in a wide range of fields to solve the above problems. However, in order to improve the fast-curing and coating properties that are characteristic of photocurable compositions, a relatively low-molecular-weight reactive monomer or organic solvent is often used in combination. Problems are toxicity, odor, flammability, irritation, etc.

【０００３】そこで、これ等の問題を解決することを目
的として、(1)活性エネルギー線硬化性化合物に共重合
等により親水性部位を導入して自己水分散性または自己
乳化性を持たせる方法、(2)従来の活性エネルギー線硬
化性化合物を低分量型もしくは高分子型の乳化剤を使用
して分散または乳化させる方法、さらには(3)前記の方
法で分散または乳化した活性エネルギー線硬化性化合物
とアクリルエマルジョンや水溶性高分子を併用する方法
等により、種々タイプの水溶性の活性エネルギー線硬化
性化合物や活性エネルギー線硬化性エマルジョンが開発
されている。しかし、これらの方法で得られるエマルジ
ョン等は分散性が不充分であったり、硬化膜の耐水性、
耐溶剤性、耐酸性、感光特性、接着性等に問題を残し未
だに実用化に至っていないのが現状である。[0003] In order to solve these problems, (1) a method of introducing a hydrophilic site into an active energy ray-curable compound by copolymerization or the like to impart self-water dispersibility or self-emulsification. , (2) a method of dispersing or emulsifying a conventional active energy ray-curable compound using a low-quantity type or high-molecular type emulsifier, and further (3) an active energy ray-curable compound dispersed or emulsified by the above method Various types of water-soluble active energy ray-curable compounds and active energy ray-curable emulsions have been developed by using a compound in combination with an acrylic emulsion or a water-soluble polymer. However, emulsions and the like obtained by these methods have insufficient dispersibility or water resistance of the cured film,
At present, it has not yet been put to practical use, leaving problems in solvent resistance, acid resistance, photosensitive properties, adhesiveness and the like.

【０００４】前記問題を解決するため、特開平２−３０
０２０４号公報には、粒子表面に重合性二重結合を導入
したエマルジョンの製造方法が開示されている。この場
合、粒子表面に重合性二重結合を導入することによっ
て、ある程度に架橋密度を高くできるものの、硬化物の
耐水性、耐溶剤性、耐酸性、感光特性、接着性等の特性
を満足するものでない。又、製造工程が複雑でコストが
高くなる難点がある。また特開平９−１５７４９５号公
報には、エマルジョン粒子が三次元架橋した高分子エマ
ルジョン及びその製造方法が開示されている。この製造
法では簡易に製造でき架橋密度も向上し有効であるが、
硬化膜の耐水性、耐溶剤性、耐酸性、感光特性、接着性
等の硬化物の特性を充分に満足するものでない。特開平
８−３０２２４０号公報には、組成物が重合反応により
エマルジョンのミセル中の重合性化合物同士が化学結合
する架橋型エマルジョン方式の光硬化性組成物が開示さ
れている。しかしながら硬化物同士の化学結合が強過ぎ
るために基材との接着性に劣り、またその他に耐水性等
の硬化物の特性を満足するものではない。さらに特許第
３０３２８５１号には水溶性高分子を用いた光硬化性エ
マルジョン樹脂組成物が開示されている。しかしながら
水溶性高分子ポリマーを使用しているために耐水性に乏
しいという問題がある。In order to solve the above problem, Japanese Patent Laid-Open No. 2-30 / 1990
No. 0204 discloses a method for producing an emulsion having a polymerizable double bond introduced into the particle surface. In this case, the crosslink density can be increased to some extent by introducing a polymerizable double bond to the particle surface, but the properties of the cured product such as water resistance, solvent resistance, acid resistance, photosensitivity, and adhesiveness are satisfied. Not something. Further, there is a problem that the manufacturing process is complicated and the cost is high. Japanese Patent Application Laid-Open No. 9-157495 discloses a polymer emulsion in which emulsion particles are three-dimensionally crosslinked, and a method for producing the same. This method is effective because it can be easily manufactured and the crosslink density is improved.
The cured film does not sufficiently satisfy the properties of the cured product such as water resistance, solvent resistance, acid resistance, photosensitive characteristics, and adhesiveness. JP-A-8-302240 discloses a cross-linkable emulsion-type photocurable composition in which polymerizable compounds in micelles of an emulsion are chemically bonded to each other by a polymerization reaction of the composition. However, since the chemical bond between the cured products is too strong, the adhesiveness to the base material is poor, and other properties such as water resistance are not satisfied. Further, Japanese Patent No. 3032851 discloses a photocurable emulsion resin composition using a water-soluble polymer. However, there is a problem that the water resistance is poor due to the use of a water-soluble polymer.

【０００５】[0005]

【発明の解決しようとする課題】従って本発明は、ＶＯ
Ｃ課題を出来る限り低減し、生産性も向上し、しかもそ
の硬化物が耐水性（耐沸水性）、耐酸性、耐溶剤性、感
光特性、接着性等に優れた光硬化性組成物およびその硬
化方法を得ることを課題とするものである。Accordingly, the present invention provides a VO
C. A photocurable composition which has as low a problem as possible, improves productivity, and has a cured product excellent in water resistance (boiling water resistance), acid resistance, solvent resistance, photosensitive properties, adhesiveness, and the like. It is an object to obtain a curing method.

【０００６】[0006]

【課題を解決するための手段】本発明者らは光硬化性組
成物およびその硬化方法について、前記課題を解決する
ために鋭意、研究、検討した結果、遂に本発明を完成す
るに到った。すなはち本発明は、反応性モノマーおよ
び／または反応性プレポリマー、光開始剤、エマルジョ
ン粒子および乳化剤を含有する光硬化性組成物において
乳化剤として可変性界面活性剤を含有することを特徴と
する光硬化性組成物。エマルジョン粒子が、ビニルモ
ノマーおよび乳化剤を反応させて得られた高分子エマル
ジョンである前記記載の光硬化性組成物。可変性界
面活性剤が熱可変性および／または光可変性界面活性剤
である前記または記載の光硬化性組成物。前記
〜のいずれかに記載の光硬化性組成物を用いて塗工し
た後、熱処理および／または活性エネルギー線照射処理
することを特徴とする光硬化性組成物の硬化方法であ
る。Means for Solving the Problems The present inventors have intensively studied, studied, and studied a photocurable composition and a method for curing the same to solve the above-mentioned problems, and have finally completed the present invention. . That is, the present invention is characterized in that a photocurable composition containing a reactive monomer and / or a reactive prepolymer, a photoinitiator, emulsion particles and an emulsifier contains a variable surfactant as an emulsifier. Photocurable composition. The photocurable composition as described above, wherein the emulsion particles are a polymer emulsion obtained by reacting a vinyl monomer and an emulsifier. The photocurable composition as described above or above, wherein the variable surfactant is a heat-variable and / or light-variable surfactant. A method for curing a photocurable composition, comprising applying the photocurable composition according to any one of the above-mentioned items, followed by heat treatment and / or irradiation with active energy rays.

【０００７】本発明において用いられるエマルジョン粒
子は、ビニルモノマーを可変性界面活性剤の存在下で乳
化重合によって得られる高分子エマルジョンであり、架
橋性エマルジョン粒子とか非架橋性高分子化合物および
高分子樹脂を可変性界面活性剤の存在下で強制乳化等に
より得られる非架橋性エマルジョン粒子等が例示され
る。The emulsion particles used in the present invention are polymer emulsions obtained by emulsion polymerization of a vinyl monomer in the presence of a variable surfactant, and include crosslinkable emulsion particles, non-crosslinkable polymer compounds and polymer resins. And non-crosslinkable emulsion particles obtained by forced emulsification in the presence of a variable surfactant.

【０００８】前記ビニルモノマーとしては、例えば、ス
チレン、α―メチルスチレン、フルオロスチレン、ビニ
ルピリジン等の芳香族モノビニル化合物、メチル（メ
タ）アクリレート、エチレ（メタ）アクリレート、ブチ
ル（メタ）アクリレート、２−エチルヘキシル（メタ）
アクリレート、２−ヒドロキシエチル（メタ）アクリレ
ート、グリシジル（メタ）アクリレート、N,N―ジメチ
ルアミノエチル（メタ）アクリレート等の（メタ）アク
リル酸エステルモノマー、（メタ）アクリロニトリル等
のシアン化ビニル化合物、（メタ）アクリル酸、マレイ
ン酸、イタコン酸等のモノもしくはジカルボン酸または
ジカルボン酸の酸無水物、（メタ）アクリルアミド等の
アミド系モノマー、さらにはスチレンスルフォン酸ナト
リウム、スルフォン化イソプレン等のイオン性モノマー
等を用いることができる。また、重合速度および重合中
の安定性等の点で許容されうる範囲内においてブタジエ
ン、イソプレン等の共役二重結合化合物や酢酸ビニル等
のビニルエステル類や４−メチルー１−ペンテン等のα
―オレフィン類も使用することができる。これらのビニ
ルモノマーは単独で使用しても良く、二種以上を組み合
わせ使用してもよい。Examples of the vinyl monomer include aromatic monovinyl compounds such as styrene, α-methylstyrene, fluorostyrene and vinylpyridine, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, Ethylhexyl (meth)
(Meth) acrylate monomers such as acrylate, 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, vinyl cyanide compounds such as (meth) acrylonitrile, Mono- or dicarboxylic acids such as (meth) acrylic acid, maleic acid, and itaconic acid or acid anhydrides of dicarboxylic acids; amide monomers such as (meth) acrylamide; and ionic monomers such as sodium styrenesulfonate and sulfonated isoprene Can be used. Further, within a range allowable in terms of polymerization rate and stability during polymerization, butadiene, conjugated double bond compounds such as isoprene, vinyl esters such as vinyl acetate, and α such as 4-methyl-1-pentene.
-Olefins can also be used. These vinyl monomers may be used alone or in combination of two or more.

【０００９】また、エマルジョン粒子を三次元架橋して
架橋密度を高くしたい場合には、架橋性ビニルモノマー
を使用することができる。架橋性ビニルモノマーとして
は、例えば、ジビニルベンゼン、エチレングリコールジ
（メタ）アクリレート、１，３−ブチレングリコールジ
（メタ）アクリレート、トリメチロールプロパン（メ
タ）アクリレート、トリメチロールエタントリ（メタ）
アクリレート、ネオペンチルグリコール（メタ）アクリ
レート、メチレンビスアクリルアミド等を例示すること
ができる。本発明では、これら架橋性ビニルモノマーの
ほかでも、特に、ジビニルベンゼン、エチレングリコー
ルジメタクリレートが好ましく使用できる。これら架橋
性ビニルモノマーは単独で使用してもよく、二種以上を
組み合わせて使用してもよい。これらの架橋性ビニルモ
ノマーは前記の単官能ビニルモノマーと混合して使用し
てもよく、その使用量は、ビニルモノマー全量に対して
２０モル％以下、好ましくは０．１〜２０モル％、より
好ましくは０．５〜１０モル％である。When it is desired to increase the crosslinking density by three-dimensionally crosslinking the emulsion particles, a crosslinkable vinyl monomer can be used. Examples of the crosslinkable vinyl monomer include divinylbenzene, ethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, trimethylolpropane (meth) acrylate, and trimethylolethanetri (meth) acrylate.
Acrylate, neopentyl glycol (meth) acrylate, methylenebisacrylamide and the like can be exemplified. In the present invention, in addition to these crosslinkable vinyl monomers, particularly, divinylbenzene and ethylene glycol dimethacrylate can be preferably used. These crosslinkable vinyl monomers may be used alone or in combination of two or more. These crosslinkable vinyl monomers may be used as a mixture with the above-mentioned monofunctional vinyl monomer, and the amount thereof is 20 mol% or less, preferably 0.1 to 20 mol%, based on the total amount of the vinyl monomers. Preferably it is 0.5 to 10 mol%.

【００１０】本発明において使用される可変性界面活性
剤とは、最初は一分子中に親水部と疎水部を有してお
り、熱および／または活性エネルギー線照射等により、
何らかの変化をして疎水性となるものである。また、機
能的には、エマルジョン粒子の形成過程において通常使
用されている乳化剤としての機能（粒子の生成、粒子の
凝集、粒子の安定化等）を具備していると同時に、熱お
よび／または活性エネルギー線照射等によって、(i)界
面活性剤の分子構造（親水部と疎水部）の親水部が化学
変化し疎水部になる、(ii)親水部と疎水部の一部が物理
的に分解し疎水部の占める割合が大きくなる、(iii)分
解した化学物質同士の架橋反応によって疎水化する、等
の性質をもつ界面活性剤のことである。[0010] The variable surfactant used in the present invention has a hydrophilic part and a hydrophobic part in one molecule at first, and is irradiated with heat and / or active energy rays or the like.
It becomes hydrophobic by some change. Functionally, it has a function as an emulsifier usually used in the process of forming emulsion particles (particle generation, particle aggregation, particle stabilization, etc.) and at the same time heat and / or activity Irradiation with energy rays, etc. causes (i) the hydrophilic part of the surfactant's molecular structure (hydrophilic part and hydrophobic part) to chemically change to a hydrophobic part, and (ii) the hydrophilic part and part of the hydrophobic part are physically decomposed. A surfactant having properties such as that the proportion occupied by the hydrophobic portion increases, and (iii) the hydrophobic substance is hydrophobized by a cross-linking reaction between decomposed chemical substances.

【００１１】具体的には、熱処理により変化する可変性
界面活性剤としては、例えば、イオン性親水部がアンモ
ニウム塩、ピリジニウム塩、スルホニウム塩、アルソニ
ウム塩、ホスホニウム塩等のイオン形成基からなる可変
性界面活性剤が例示され、このイオン形成基が熱処理に
よって熱分解し、前記(i)〜(iii)の何れかに変化するこ
とによって疎水性となるものである。Specifically, as the variable surfactant which is changed by heat treatment, for example, a variable surfactant in which the ionic hydrophilic part comprises an ion-forming group such as an ammonium salt, a pyridinium salt, a sulfonium salt, an arsonium salt, a phosphonium salt or the like. Surfactants are exemplified, and the ion-forming group becomes hydrophobic by being thermally decomposed by heat treatment and changed to any of the above (i) to (iii).

【００１２】一方、活性エネルギー線照射による光可変
性界面活性剤には、活性エネルギー線照射によって化学
物質のそのものが光分解するもの、或いは活性エネルギ
ー線照射によって化学物質が酸発生剤または塩基性発生
剤を介して分解するものが挙げられる。例えば、化学物
質そのものが光分解するものとしては、α―ケトカルボ
ン酸塩、β―ケトカルボン酸塩、フェニル酢酸塩、ニト
ロフェニル酢酸塩、アゾスルホネート塩等が界面活性剤
の構造骨格の一部に有する可変性界面活性剤を例示する
ことができる。また、活性エネルギー線照射によって酸
発生剤を介して分解する化学物質としては、例えば、ジ
オキシラン、１，３−ジオキサン環、シロキサン、ポリ
エチレングリコールモノメチルエステルアセタール等が
界面活性剤の構造骨格に一部に有する可変性界面活性剤
が例示され、塩基性発生剤を介して分解する化学物質と
しては、例えば、アセタール型ビス（アンモニウムブロ
マイド）を例示することができる。On the other hand, a photo-variable surfactant by irradiation with an active energy ray includes a substance in which a chemical substance itself is photodegraded by irradiation with an active energy ray, or a chemical substance which is converted into an acid generator or a basic substance by irradiation with an active energy ray. One that decomposes via an agent is included. For example, as the chemical substance itself photodecomposes, α-ketocarboxylate, β-ketocarboxylate, phenylacetate, nitrophenylacetate, azosulfonate, etc. are part of the structural skeleton of the surfactant. A variable surfactant can be exemplified. Further, as the chemical substance which is decomposed via an acid generator by irradiation with active energy rays, for example, dioxirane, 1,3-dioxane ring, siloxane, polyethylene glycol monomethyl ester acetal, etc. are partially included in the structural skeleton of the surfactant. Examples of the chemical substance that decomposes via a basic generator include an acetal-type bis (ammonium bromide).

【００１３】これらの可変性界面活性剤は、非架橋性高
分子化合物および高分子樹脂を強制乳化することによっ
て得られる非架橋性エマルジョン粒子にも使用できる。
非架橋性高分子化合物および高分子樹脂としては、具体
的にエポキシ化合物、エポキシ樹脂、ポリエステル樹
脂、ウレタン樹脂、ポリウレア樹脂、酢酸ビニル等が例
示できる。これらは、可変性界面活性剤の存在下で後記
する反応性モノマーや光開始剤、水溶性有機溶剤および
水からなる混合物を強制攪拌することによってエマルジ
ョン粒子が得られ、そして熱処理および／または活性エ
ネルギー線照射をすることによって疎水性にすることが
できる。[0013] These variable surfactants can also be used for non-crosslinkable emulsion particles obtained by forcibly emulsifying a non-crosslinkable polymer compound and a polymer resin.
Specific examples of the non-crosslinkable polymer compound and the polymer resin include an epoxy compound, an epoxy resin, a polyester resin, a urethane resin, a polyurea resin, and vinyl acetate. These are obtained by forcibly stirring a mixture of a reactive monomer and a photoinitiator, which will be described later, a water-soluble organic solvent and water in the presence of a variable surfactant, to obtain emulsion particles. It can be made hydrophobic by irradiating with a line.

【００１４】なお、可変性界面活性剤を用いてエマルジ
ョン粒子を製造する時の使用量は、エマルジョン粒子の
粒子径、安定性、架橋密度さらには硬化物の特性等によ
り任意に含有させることができるが、その配合量は、ビ
ニルモノマー全量に対して０．０１〜８０重量％程度、
好ましくは０．１〜５０重量％である。更に好ましくは
０．１〜１０重量％である。なお、平均粒子径が１００
nm以上のエマルジョン粒子の放置安定性をよくするに
は、可変性界面活性剤は５重量％以上使用するのが好ま
しい。The amount of emulsion particles produced using the variable surfactant can be arbitrarily selected depending on the particle size, stability, crosslink density, and properties of the cured product of the emulsion particles. However, the compounding amount is about 0.01 to 80% by weight based on the total amount of the vinyl monomer,
Preferably it is 0.1 to 50% by weight. More preferably, it is 0.1 to 10% by weight. The average particle diameter is 100
In order to improve the storage stability of the emulsion particles having a size of nm or more, it is preferable to use 5% by weight or more of the variable surfactant.

【００１５】可変性界面活性を用いて乳化重合する時の
温度は、５０〜９５℃程度、好ましくは６５〜８５℃で
ある。また乳化重合時の濃度は、ビニルモノマーと可変
性界面活性剤を合わせた固形分の割合が１０〜５０重量
％程度、好ましくは１５〜４０重量％の範囲で行なわれ
る。The temperature at the time of emulsion polymerization using variable surface activity is about 50 to 95 ° C., preferably 65 to 85 ° C. The concentration at the time of emulsion polymerization is such that the ratio of the solid content of the vinyl monomer and the variable surfactant is about 10 to 50% by weight, preferably 15 to 40% by weight.

【００１６】また、本発明の可変性界面活性剤を用いて
乳化重合で架橋性エマルジョン粒子を得るに使用される
重合開始剤としては、通常の乳化重合で用いられるもの
であれば特に制限を受けない。例えば、過硫酸カリウ
ム、過硫酸ナトリウム、過硫酸アンモニウム等の過硫酸
塩、過酸化水素、有機過酸化物、水性のアゾ系開始剤等
の水溶性ラジカル重合開始剤等を単独で、または前記過
硫酸塩等と亜硫酸水素ナトリウム、チオ硫酸水素ナトリ
ウム、アスコルビン酸等の各種還元剤と組み合わせたレ
ドックス系重合開始剤等を使用できる。重合開始剤の使
用量は、ビニルモノマー全量に対して０．００５〜５モ
ル％の範囲とするのが好ましい。The polymerization initiator used for obtaining crosslinkable emulsion particles by emulsion polymerization using the variable surfactant of the present invention is not particularly limited as long as it is used in ordinary emulsion polymerization. Absent. For example, potassium persulfate, sodium persulfate, persulfates such as ammonium persulfate, hydrogen peroxide, organic peroxides, water-soluble radical polymerization initiators such as aqueous azo initiators alone or the above persulfate A redox polymerization initiator or the like in which a salt or the like is combined with various reducing agents such as sodium hydrogen sulfite, sodium thiosulfate, and ascorbic acid can be used. The amount of the polymerization initiator used is preferably in the range of 0.005 to 5 mol% based on the total amount of the vinyl monomer.

【００１７】以上に説明した本発明の光硬化性組成物
は、特開平９−１５７４９５号公報等に記載された製造
方法等により架橋性エマルジョン粒子を製造することが
できる。この方法で得られた架橋性エマルジョン粒子の
平均粒子径は０．０５〜５００μｍ程度の粒子を得るこ
とができる。The photocurable composition of the present invention described above can be used to produce crosslinkable emulsion particles by the production method described in JP-A-9-157495 and the like. Particles having an average particle diameter of about 0.05 to 500 μm of the crosslinkable emulsion particles obtained by this method can be obtained.

【００１８】本発明では、硬化物の耐水性、耐酸性、耐
溶剤性、感光特性を向上させるために前記のエマルジョ
ン粒子内部および外部に以下の反応性プレポリマーや反
応性モノマーを含有することができる。具体的には、反
応性プレポリマーとしてエポキシ（メタ）アクリレー
ト、ポリウレタン（メタ）アクリレート、ポリエステル
（メタ）アクリレート、ポリエーテル（メタ）アクリレ
ート、シリコン（メタ）アクリレート、ポリブタジエン
（メタ）アクリレート、ポリアミド（メタ）アクリレー
ト等を例示できる。また、反応性モノマーとしては、ス
チレン、酢酸ビニル、N―ビニルピロリオン等のビニル
モノマー、ブチルアクリレート、２−エチルヘキシルア
クリレート、n−ヘキシルアクリレート、シクロヘキシ
ルアクリレート、n―ドデシルアクリレート、イソホロ
ニルアクリレート、ジシクロペンテニルオキシエチルア
クリレート、フェノキシエチルアクリレート等の単官能
モノマー、１，４−ブタンジオールジアクリレート、
１，６−ヘキサンジオールジアクリレート、ジュエチレ
ングリコールジアクリレート、ネオペンチルグリコール
ジアクリレート、ポリエチレングリコールジアクリレー
ト、トリプロピレングリコールジアクリレート、ビスフ
ェノールＡジエトキシジアクリレート、トリメチロール
プロパントリアクリレート、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等の多
官能モノマーを例示できる。これらの反応性モノマーま
たは反応性プレポリマーの使用量は、光硬化性組成物に
通常０．１〜２００重量％程度、好ましくは１〜１００
重量％の範囲である。In the present invention, in order to improve the water resistance, acid resistance, solvent resistance and photosensitivity of the cured product, the following reactive prepolymer or reactive monomer may be contained inside and outside the emulsion particles. it can. Specifically, epoxy (meth) acrylate, polyurethane (meth) acrylate, polyester (meth) acrylate, polyether (meth) acrylate, silicon (meth) acrylate, polybutadiene (meth) acrylate, polyamide (meth) are used as reactive prepolymers. And acrylate). Further, as the reactive monomer, styrene, vinyl acetate, vinyl monomers such as N-vinyl pyrrolion, butyl acrylate, 2-ethylhexyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, n-dodecyl acrylate, isophoronyl acrylate, Monofunctional monomers such as cyclopentenyloxyethyl acrylate and phenoxyethyl acrylate, 1,4-butanediol diacrylate,
1,6-hexanediol diacrylate, deethylene glycol diacrylate, neopentyl glycol diacrylate, polyethylene glycol diacrylate, tripropylene glycol diacrylate, bisphenol A diethoxy diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, Examples thereof include polyfunctional monomers such as pentaerythritol tetraacrylate and dipentaerythritol hexaacrylate. The amount of these reactive monomers or reactive prepolymers used is usually about 0.1 to 200% by weight, preferably 1 to 100% by weight in the photocurable composition.
% By weight.

【００１９】また、本発明の光硬化性組成物を紫外線に
より硬化させるには、光重合性開始剤を含有させる。一
方、電子線で硬化させる場合には光開始剤は不要とされ
る。光開始剤としては、通常紫外線硬化性化合物に使用
されているものを使用できる。例えば、アセトフェノ
ン、ベンゾフェノン、ベンゾインエーテル、クロロアセ
トフェノン、ジエトキシアセトフェノン、α―アミノア
セトフェノン、ベンジルメチルケタール、チオキサント
ン、α―アシルオキシムエステル、アシルホスフィンオ
キシド、グリオキシエステル、３−ケトクマリン、２−
エチルアンスラキノン、カンファーキノン、ミヒラーケ
トン等を例示できる。これらの光開始剤は、エマルジョ
ン組成物中に通常０．１〜２０重量％、好ましくは１〜
１０重量％範囲で使用される。In order to cure the photocurable composition of the present invention with ultraviolet rays, a photopolymerizable initiator is contained. On the other hand, when curing with an electron beam, a photoinitiator is not required. As the photoinitiator, those usually used for ultraviolet curable compounds can be used. For example, acetophenone, benzophenone, benzoin ether, chloroacetophenone, diethoxyacetophenone, α-aminoacetophenone, benzylmethyl ketal, thioxanthone, α-acyloxime ester, acylphosphine oxide, glyoxyester, 3-ketocoumarin, 2-ketocoumarin
Examples thereof include ethylanthraquinone, camphorquinone, and Michler's ketone. These photoinitiators are usually contained in the emulsion composition in an amount of 0.1 to 20% by weight, preferably 1 to 20% by weight.
Used in the range of 10% by weight.

【００２０】本発明の光硬化性組成物には、水溶性有機
溶剤を混合しても良い。水溶性有機溶剤としては、例え
ばメタノール、エタノール、プロパノール、イソプロパ
ノール、アセトン、メチルエチルケトン、テトラヒドロ
フラン、ジオキサン等の水と親和性の良い有機溶剤を用
いることができる。特にエマルジョン組成物を共沸等に
除去できるものが好ましい。水溶性有機溶剤の配合量は
組成物中に０．１〜５０重量％、好ましくは１〜１０重
量％の範囲で配合できる。The photocurable composition of the present invention may contain a water-soluble organic solvent. As the water-soluble organic solvent, for example, an organic solvent having a high affinity for water such as methanol, ethanol, propanol, isopropanol, acetone, methyl ethyl ketone, tetrahydrofuran, dioxane and the like can be used. Particularly, those which can remove the emulsion composition azeotropically or the like are preferable. The compounding amount of the water-soluble organic solvent can be 0.1 to 50% by weight, preferably 1 to 10% by weight in the composition.

【００２１】以上、前記の光硬化性組成物は、水分散液
として使用できる。水分散液のエマルジョン粒子への添
加方法は、一括添加、連続添加もしくは間欠添加または
これらを組み合わせることができる。また、水分散液を
添加する際のエマルジョン粒子の濃度は、１０〜５０重
量％程度、好ましくは１５〜４０重量％である。添加時
の温度は２０〜７０℃程度であり、好ましくは３０〜５
０℃である。As described above, the photocurable composition can be used as an aqueous dispersion. The method of adding the aqueous dispersion to the emulsion particles may be batch addition, continuous addition, intermittent addition, or a combination thereof. The concentration of the emulsion particles when the aqueous dispersion is added is about 10 to 50% by weight, preferably 15 to 40% by weight. The temperature at the time of addition is about 20 to 70 ° C, preferably 30 to 5 ° C.
0 ° C.

【００２２】なお、可変性界面活性剤の存在下で非架橋
性高分子化合物および高分子樹脂を用いて非架橋性エマ
ルジョン粒子を作製する場合は、非架橋高分子化合物お
よび高分子樹脂と前記可変性界面活性剤、反応性モノマ
ー、光開始剤、水溶性有機溶剤および水とを混合し強制
攪拌することによってエマルジョン粒子を作製すること
ができる。When the non-crosslinkable emulsion particles are prepared using the non-crosslinkable polymer compound and the polymer resin in the presence of the variable surfactant, the non-crosslinkable polymer compound and the polymer resin are mixed with the variable crosslinkable polymer compound and the polymer resin. Emulsion particles can be prepared by mixing a water-soluble surfactant, a reactive monomer, a photoinitiator, a water-soluble organic solvent, and water and forcibly stirring them.

【００２３】次に本発明光硬化性組成物を用いて硬化物
を得る硬化方法としては、熱処理および／または活性エ
ネルギー線照射による硬化方法が挙げられる。具体的に
は、前記の熱可変性界面活性剤を用いた場合の熱処理の
温度としては、１２０〜２００℃の範囲、好ましくは１
３０〜１５０℃の範囲で処理することによってイオン形
成基が分解させる。１２０℃以下の温度では熱分解が不
充分となり目的とする硬化物を得ることができ難い。ま
た、前記の光可変性界面剤を用いた場合の活性エネルギ
ー線としての紫外線は１５０〜５００ｍμの波長、特に
３００〜４００ｍμの波長領域のものが有効である。使
用される光源としては低圧水銀灯、高圧水銀灯、超高圧
水銀灯、カーボンアーク灯、紫外線蛍光灯、ケミカルラ
ンプ、キセノンランプ、ジルコニウムランプ等が望まし
い。また、本発明からなる光硬化性組成物を用いて硬化
物を得る方法としては、６０〜１１０℃の範囲の温度で
予備乾燥した後、紫外線によって照射し、更に１２０〜
２００℃の範囲の温度で乾燥する方法も採用できる。Next, as a curing method for obtaining a cured product using the photocurable composition of the present invention, a curing method by heat treatment and / or irradiation with active energy rays can be mentioned. Specifically, the temperature of the heat treatment when the above-mentioned heat-variable surfactant is used is in the range of 120 to 200 ° C, preferably 1 to 200 ° C.
By treating at a temperature in the range of 30 to 150 ° C., the ion-forming groups are decomposed. At a temperature of 120 ° C. or lower, the thermal decomposition becomes insufficient, and it is difficult to obtain a desired cured product. In addition, when the above-mentioned photo-variable surfactant is used, ultraviolet rays as active energy rays having a wavelength of 150 to 500 mμ, particularly a wavelength region of 300 to 400 mμ are effective. The light source used is preferably a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a carbon arc lamp, an ultraviolet fluorescent lamp, a chemical lamp, a xenon lamp, a zirconium lamp, or the like. Further, as a method for obtaining a cured product using the photocurable composition according to the present invention, after preliminarily drying at a temperature in the range of 60 to 110 ° C, irradiation with ultraviolet light,
A method of drying at a temperature in the range of 200 ° C. can also be adopted.

【００２４】本発明からなる光硬化性組成物は、例えば
ポリエチレンテレフタレートフィルム、ポリエチレンフ
ィルム、ポリプロピレンフィルム、ポリスチレンフィル
ム、ポリイミドフィルム、ポリアミドイミドフィルム、
ポリイミド銅張積層板、リジッド板、ガラス板、紙等の
基材に塗工して前記方法にて硬化し硬化物を得ることが
できるが、これ等に限定されるものではない。The photocurable composition according to the present invention may be, for example, a polyethylene terephthalate film, a polyethylene film, a polypropylene film, a polystyrene film, a polyimide film, a polyamideimide film,
A cured product can be obtained by coating on a substrate such as a polyimide copper-clad laminate, a rigid plate, a glass plate, and paper and curing by the above method, but is not limited thereto.

【００２５】塗工方法としては、例えばグラビアコート
方式、キスコート方式、ディップ方式、スプレーコート
方式、カーテンコート方式、エアナイフコート方式、ブ
レードコート方式、リバースロールコート方式、スクリ
ーン印刷方式、静電スプレーコー方式等の方法が採用で
きるがこれ等に限定するものではない。Examples of the coating method include a gravure coating method, a kiss coating method, a dip method, a spray coating method, a curtain coating method, an air knife coating method, a blade coating method, a reverse roll coating method, a screen printing method, and an electrostatic spray coating method. However, the present invention is not limited thereto.

【００２６】なお、本発明の光硬化性組成物には任意の
色素、顔料、レべリング剤、消泡剤、充填剤等を添加す
ることができるが特に限定するものではない。The photocurable composition of the present invention can contain any dye, pigment, leveling agent, defoaming agent, filler, etc., but is not particularly limited.

【００２７】[0027]

【発明の実施の形態】本発明の光硬化性組成物およびそ
の硬化方法の一実施態様としては、(I)主として反応性
モノマー、光開始剤および可変性界面活性剤からなる光
硬化性エマルジョンを得る。(II)このエマルジョンをポ
リイミドフィルム銅張積層板の銅箔表面に乾燥処理後の
厚みが約１０ｇ／m2になるように塗工し、８０℃２０分
で乾燥する。(III)得られた塗工膜面へ３ＫＷ超高圧水
銀灯を用い５００mj／ｃm2の照度で光硬化させる。(IV)
更に、１５０℃３０分乾燥する。(V)これ等の硬化法に
よって得られた硬化膜を評価項目に沿って評価する。BEST MODE FOR CARRYING OUT THE INVENTION As one embodiment of the photocurable composition of the present invention and a method for curing the same, (I) a photocurable emulsion mainly comprising a reactive monomer, a photoinitiator and a variable surfactant is used. obtain. (II) This emulsion is applied on the copper foil surface of the polyimide film copper-clad laminate so that the thickness after drying treatment is about 10 g / m 2 , and dried at 80 ° C. for 20 minutes. (III) The obtained coating film surface is photo-cured at an illuminance of 500 mj / cm 2 using a 3 KW ultra-high pressure mercury lamp. (IV)
Further, it is dried at 150 ° C. for 30 minutes. (V) The cured films obtained by these curing methods are evaluated according to the evaluation items.

【００２８】[0028]

【実施例】以下、本発明を実施例を用いて本発明を具体
的に説明するが、本発明はこれらの実施例に限定される
ものではない。なお実施例中に、部とあるのは重量部を
意味する。また、実施例中における評価項目と方法は、
次に述べる方法による。 １）耐水性（耐沸水性）：ポリイミドフィルム銅張積層
板の銅箔上に硬化膜を有する試料を８０℃〜９０℃の沸
水中に１時間浸漬させたあと、硬化膜の表面の水滴を拭
き取り、ＪＩＳＫ５４００碁盤目剥離試験法により銅箔
との接着性を評価した。１００／１００：○ ８０／１
００：△ ８０以下／１００：×とした。 ２）耐酸性：１０％塩酸液と１０％硫酸液を用いて試料
を常温３０分間浸漬させ、１）と同様な方法で評価し
た。 ３）耐溶剤性：トルエンとアセトンを用いて試料を常温
３０分間浸漬させ１）と同様な方法で評価した。 ４）鉛筆硬度：銅箔上の硬化膜を、ＪＩＳＫ５４００鉛
筆引っ掛け試験法により評価した。この測定値から硬化
膜の感光性の良否を判断した。 ≧Ｈ:○ ≧Ｂ:△ Ｆ＜:× ５）エマルジョン粒子径：ＣＯＵＬＴＥＲ ＭＯＤＥＬ
Ｎ４ＳＤ（ＣＯＵＬＴＥＲ ＥＬＥＣＴＲＯＮＩＣＳ，
ＩＮＣ製）を用いてエマルジョン粒子径を測定した。 ６）電気絶縁抵抗：銅箔をエッチングしてなるＩＰＣパ
ターン上に前記方法により硬化膜を形成し、ＪＩＳ Ｃ
００２２高温高湿試験法により、５０℃８５％ＲＨ１６
０時間の処理をし、ＨＩＧＨ ＲＥＳＩＳＴＡＮＣＥ
ＭＥＴＥＲ（横河・ヒューレット・パッカード（株））
の測定器で５００Ｖ１分間印加後の絶縁抵抗を測定し
た。EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples. In the examples, “parts” means “parts by weight”. The evaluation items and methods in the examples are as follows:
The following method is used. 1) Water resistance (boiling water resistance): A sample having a cured film on a copper foil of a polyimide film copper-clad laminate is immersed in boiling water at 80 ° C. to 90 ° C. for 1 hour, and then water droplets on the surface of the cured film are removed. Wiping was performed, and the adhesion to the copper foil was evaluated by a JIS K5400 cross-cut peel test. 100/100: ○ 80/1
00: 80 or less / 100: x 2) Acid resistance: A sample was immersed in a 10% hydrochloric acid solution and a 10% sulfuric acid solution at room temperature for 30 minutes, and evaluated in the same manner as in 1). 3) Solvent resistance: A sample was immersed in normal temperature for 30 minutes using toluene and acetone, and evaluated in the same manner as in 1). 4) Pencil hardness: The cured film on the copper foil was evaluated by the JIS K5400 pencil hook test method. From the measured values, the quality of the photosensitivity of the cured film was determined. ≧ H: ○ ≧ B: △ F <: × 5) Emulsion particle size: COULTER MODEL
N4SD (COULTER ELECTRONICS,
INC.) Was used to measure the emulsion particle diameter. 6) Electric insulation resistance: A cured film is formed on an IPC pattern formed by etching a copper foil by the above method, and the JIS C
According to the high-temperature high-humidity test method, 50 ° C, 85% RH16
0 hour processing, HIGH RESISTANCE
METER (Yokogawa Hewlett-Packard Co., Ltd.)
Was used to measure the insulation resistance after applying 500 V for 1 minute.

【００２９】実施例１ 攪拌器、窒素導入管、温度計、還流冷却管を取り付けた
１リットル反応器に、イオン交換水４４０ｇ、硫酸銅
０．２４ｍｇ、α―ケトカルボン酸塩型界面活性剤２２
ｇを入れて攪拌した後、２８％アンモニア水溶液でＰＨ
を３．５に調整した。さらに、メチルメタクリレート２
８．８ｇ、ブチルアクリレート１２．３ｇとチオ硫酸ナ
トリウム０．４ｇを加え窒素ガスを通じながら３０℃で
攪拌、混合した。次いで５％過硫酸アンモニウム水溶液
１４ｇを添加することによって重合を開始させた。重合
による発熱が開始した段階でメチルメタクリレート１３
１ｇ、ブチルアクリレート５６．１ｇの混合液を２時間
で滴下した。この際、温度が６０℃を越えないように滴
下速度を調整した。滴下終了後、６０℃で３時間保温し
て平均粒子径９０ｎｍのエマルジョン粒子を得た。Example 1 In a 1-liter reactor equipped with a stirrer, a nitrogen inlet tube, a thermometer and a reflux condenser, 440 g of ion-exchanged water, 0.24 mg of copper sulfate, α-ketocarboxylate type surfactant 22 were added.
g and stirred.
Was adjusted to 3.5. Furthermore, methyl methacrylate 2
8.8 g, 12.3 g of butyl acrylate and 0.4 g of sodium thiosulfate were added, and stirred and mixed at 30 ° C. while passing nitrogen gas. Then, polymerization was started by adding 14 g of a 5% aqueous solution of ammonium persulfate. At the stage when the heat generation due to the polymerization starts, methyl methacrylate 13
A mixture of 1 g and 56.1 g of butyl acrylate was added dropwise over 2 hours. At this time, the dropping speed was adjusted so that the temperature did not exceed 60 ° C. After the completion of the dropwise addition, the mixture was kept at 60 ° C. for 3 hours to obtain emulsion particles having an average particle diameter of 90 nm.

【００３０】次に、得られたエマルジョンにイオン交換
水を９６３．８ｇを添加して濃度を１５％に調整した
後、４０℃まで冷却した。この１５％濃度のエマルジョ
ンにペンタエリスリトールテトラアクリレートＰＥ−４
Ａ（共栄社化学（株）製）５０ｇ、光開始剤ダルキュア
１１７３（メルク（株）製）１．５ｇ、α―ケトカルボ
ン酸塩型界面活性剤０．１ｇおよびイオン交換水９１．
２ｇをホモジナイザー（ＪＡＮＫＥ＆ＫＵＮＫＥＬ
（株）製）で乳化（１００００ｒｐｍ，５分）させた分
散液を添加して、室温で５時間攪拌することによって平
均粒子径９５ｎｍの光可変性界面活性剤を含有する光硬
化性組成物を得た。Next, 963.8 g of ion-exchanged water was added to the obtained emulsion to adjust the concentration to 15%, and then cooled to 40 ° C. Pentaerythritol tetraacrylate PE-4 was added to this 15% concentration emulsion.
A (manufactured by Kyoeisha Chemical Co., Ltd.), 50 g of photoinitiator Dulcure 1173 (manufactured by Merck Ltd.), 0.1 g of α-ketocarboxylate type surfactant and ion-exchanged water
2 g of homogenizer (JANKE & KUNKEL)
A dispersion liquid emulsified (10000 rpm, 5 minutes) was added thereto, and the mixture was stirred at room temperature for 5 hours to obtain a photocurable composition containing a photovariable surfactant having an average particle diameter of 95 nm. Obtained.

【００３１】実施例２ 実施例１で使用した光可変性界面活性剤に代わって、光
可変性界面活性剤としてジアゾスルホン酸塩型界面活性
剤を使用した以外は全て同じ方法で平均粒子径９５ｎｍ
の光可変性界面活性剤を含有する光硬化性組成物を得
た。Example 2 An average particle diameter of 95 nm was obtained in the same manner except that a diazosulfonate type surfactant was used as the light variable surfactant instead of the light variable surfactant used in Example 1.
A photo-curable composition containing the photo-variable surfactant was obtained.

【００３２】実施例３ 実施例１で使用した光可変性界面活性剤に代わって、フ
ェニル酢酸塩型界面活性剤を使用した以外は全て同じ方
法で平均粒子径９７ｎｍの光可変性界面活性剤を含有す
る光硬化性組成物を得た。Example 3 A light-variable surfactant having an average particle diameter of 97 nm was prepared in the same manner except that a phenylacetate-type surfactant was used instead of the light-variable surfactant used in Example 1. The resulting photocurable composition was obtained.

【００３３】実施例４ 実施例１で使用した光可変性界面活性剤に代わって、活
性エネルギー線の照射によって酸発生剤を介して分解す
る酸分解型界面活性剤として、特殊な疎水基と酸化エチ
レン鎖の親水基からなる界面活性剤ＴＲＩＴＯＮ ＳＰ
（ユニオン・カーバイド日本（株）製）を用いた以外は
全て同様な方法で平均粒子径９７ｎｍの酸分解型界面活
性剤を含有する光硬化性組成物を得た。Example 4 In place of the photo-variable surfactant used in Example 1, an acid-decomposable surfactant which decomposes via an acid generator upon irradiation with an active energy ray, has a special hydrophobic group and an oxidizing agent. Triton SP, a surfactant consisting of a hydrophilic group in the ethylene chain
A photocurable composition containing an acid-decomposable surfactant having an average particle size of 97 nm was obtained in the same manner except that (Union Carbide Japan Co., Ltd.) was used.

【００３４】実施例５ 実施例４で使用した酸分解型界面活性剤に代わって活性
エネルギー線の照射によって塩基性発生剤を介して分解
する塩基性分解型界面活性剤として、アセタール型ビス
（アンモニウムブロマイド）系の界面活性剤を使用した
以外、実施例１と同様な方法で平均粒子径１００ｎｍの
塩基性分解型界面活性剤を含有する光硬化性組成物を得
た。Example 5 In place of the acid-decomposable surfactant used in Example 4, acetal-type bis (ammonium) was used as a basic decomposable surfactant which decomposes via a basic generator by irradiation with active energy rays. A photocurable composition containing a basic decomposition type surfactant having an average particle diameter of 100 nm was obtained in the same manner as in Example 1 except that a bromide-based surfactant was used.

【００３５】実施例６ 次に、熱可変性界面活性剤として、アンモニウム塩型界
面活性剤を使用した以外、実施例１と同様な方法で平均
粒子径９５ｎｍの熱可変性界面活性剤を含有する光硬化
性組成物を得た。Example 6 Next, a heat-variable surfactant having an average particle diameter of 95 nm is contained in the same manner as in Example 1 except that an ammonium salt-type surfactant is used as the heat-variable surfactant. A photocurable composition was obtained.

【００３６】実施例７ また、熱可変性界面活性剤として、スルホニウム塩型界
面活性剤を使用した以外、実施例１と同様な方法で平均
粒子径９５ｎｍの熱可変性界面活性剤を含有する光硬化
性組成物を得た。Example 7 In the same manner as in Example 1, except that a sulfonium salt-type surfactant was used as the heat-variable surfactant, a light containing a heat-variable surfactant having an average particle diameter of 95 nm was used. A curable composition was obtained.

【００３７】比較例１ 実施例１で使用した可変性界面活性剤に代わって、通
常、乳化剤として使用されるラウリルベンゼンスルホン
酸ナトリウムを使用した以外、実施例１と同様な方法で
平均粒子径８０ｎｍの光硬化性組成物を得た。Comparative Example 1 An average particle diameter of 80 nm was obtained in the same manner as in Example 1 except that sodium laurylbenzenesulfonate, which is usually used as an emulsifier, was used instead of the variable surfactant used in Example 1. Was obtained.

【００３８】比較例２ 実施例１で使用した可変性界面活性に代わって、通常に
乳化剤として使用されるラウリル硫酸ナトリウムを使用
した以外、実施例１と同様な方法で平均粒子径８５ｎｍ
の光硬化性組成物を得た。Comparative Example 2 An average particle size of 85 nm was obtained in the same manner as in Example 1 except that sodium lauryl sulfate, which is usually used as an emulsifier, was used instead of the variable surface activity used in Example 1.
Was obtained.

【００３９】実施例１〜７および比較例１〜２によって
得られたエマルジョン組成物を、それぞれ乾燥処理後の
厚みが１０ｇ／ｍ2になるよう１ＯＺのポリイミドフィ
ルム銅張積層板に塗工した。そして、８０℃２０分で乾
燥させ、３ＫＷ高圧水銀灯を用いて５００ｍｊ／cｍ2の
照度で光硬化させ、得られた光硬化膜を１５０℃３０分
熱処理し硬化膜を得た。これ等の硬化膜を評価項目に沿
って評価した。なお、電気絶縁抵抗の測定は、予めポリ
イミドフィルム銅張積層板を用いてＩＰＣ評価パターン
にエッチング加工された配線パターンを用い、塗工・硬
化して得たものを使用し評価した。その評価結果、実施
例１〜７、比較例１〜２の結果を表１に示す。The emulsion compositions obtained in Examples 1 to 7 and Comparative Examples 1 and 2 were coated on a 10 OZ polyimide film copper-clad laminate so that the thickness after drying was 10 g / m 2 . Then, the film was dried at 80 ° C. for 20 minutes, and was photocured with a 3 KW high-pressure mercury lamp at an illuminance of 500 mj / cm 2. The obtained photocured film was heat-treated at 150 ° C. for 30 minutes to obtain a cured film. These cured films were evaluated according to the evaluation items. In addition, the measurement of the electric insulation resistance was evaluated by using a wiring pattern obtained by coating and curing a wiring pattern which was previously etched into an IPC evaluation pattern using a polyimide film copper-clad laminate. Table 1 shows the evaluation results, and the results of Examples 1 to 7 and Comparative Examples 1 and 2.

【００４０】[0040]

【表１】 [Table 1]

【００４１】[0041]

【発明の効果】以上、表１からも明らかなように、本発
明の光硬化性組成物およびその硬化方法からなる硬化物
は、耐水性（耐沸水性）、耐酸性、耐溶剤性、感光特
性、接着性、電気絶縁性に優れ、例えば、塗料、印刷イ
ンキ、表面コート剤、フォトレジスト、接着剤等の用途
に使用できこれ等の産業界に寄与すること大である。As is clear from Table 1, the photocurable composition of the present invention and the cured product obtained by the curing method are water-resistant (boiling water-resistant), acid-resistant, solvent-resistant and photosensitive. It has excellent properties, adhesiveness, and electrical insulation, and can be used for, for example, paints, printing inks, surface coating agents, photoresists, adhesives, etc., and greatly contributes to these industries.

───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０９Ｄ 4/00 Ｃ０９Ｄ 4/00 Ｆターム(参考） 4J011 PA29 PA36 PA40 PA43 PA45 PA46 PA50 PA63 PA64 PA65 PA69 PA70 PA74 PA76 PA90 PA99 PB40 PC08 QA03 QA08 QA09 QA12 QA13 QA22 QA23 QA24 QA33 QA45 QA46 QB05 QB14 QB16 QB18 QB19 QB24 QB25 RA03 RA04 RA05 RA08 RA10 SA02 SA12 SA15 SA16 SA17 SA18 SA19 SA22 SA25 SA28 SA33 SA54 SA61 SA62 SA63 SA64 SA65 TA08 TA10 UA01 UA03 UA08 VA01 VA02 WA01 WA02 WA06 4J027 AA04 AB03 AB10 AC06 AD02 AE01 AF05 AG33 AJ08 BA02 BA04 BA05 BA07 BA13 BA19 BA24 BA26 BA27 CA02 CA03 CA10 CA24 CA25 CA26 CA27 CA29 CB10 CC02 CC05 CC06 CD08 CD09 CD10 4J038 EA012 FA011 FA222 KA03 KA09 MA08 MA10 PA17 PA19──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI theme coat ゛ (reference) C09D 4/00 C09D 4/00 F term (reference) 4J011 PA29 PA36 PA40 PA43 PA45 PA46 PA50 PA63 PA64 PA65 PA69 PA70 PA74 PA76 PA90 PA99 PB40 PC08 QA03 QA08 QA09 QA12 QA13 QA22 QA23 QA24 QA33 QA45 QA46 QB05 QB14 QB16 QB18 QB19 QB24 QB25 RA03 RA04 RA05 RA08 RA10 SA02 SA12 SA15 SA16 SA17 SA18 SA19 SA22 SA03 SA08 SA08 SA33 SA08 SA09 VA01 VA02 WA01 WA02 WA06 4J027 AA04 AB03 AB10 AC06 AD02 AE01 AF05 AG33 AJ08 BA02 BA04 BA05 BA07 BA13 BA19 BA24 BA26 BA27 CA02 CA03 CA10 CA24 CA25 CA26 CA27 CA29 CB10 CC02 CC05 CC06 CD08 CD09 CD10 4J038 EA012 FA01 FA22 MA01

Claims (4)

【特許請求の範囲】[Claims] 【請求項１】反応性モノマーおよび／または反応性プレ
ポリマー、光開始剤、エマルジョン粒子および乳化剤を
含有する光硬化性組成物において乳化剤として可変性界
面活性剤を含有することを特徴とする光硬化性組成物。Claims: 1. A photocurable composition comprising a reactive monomer and / or a reactive prepolymer, a photoinitiator, emulsion particles and an emulsifier, comprising a variable surfactant as an emulsifier. Composition. 【請求項２】エマルジョン粒子が、ビニルモノマーおよ
び乳化剤を反応させて得られた高分子エマルジョンであ
って、乳化剤として可変性界面活性剤を含有することを
特徴とする請求項１記載の光硬化性組成物。2. The photocurable composition according to claim 1, wherein the emulsion particles are a polymer emulsion obtained by reacting a vinyl monomer and an emulsifier, and contain a variable surfactant as an emulsifier. Composition. 【請求項３】可変性界面活性剤が熱可変性および／また
は光可変性界面活性剤である請求項１または２記載の光
硬化性組成物。3. The photocurable composition according to claim 1, wherein the variable surfactant is a heat variable and / or light variable surfactant. 【請求項４】請求項１〜３のいずれかに記載の光硬化性
組成物を用いて塗工した後、熱処理および／または活性
エネルギー線照射処理することを特徴とする光硬化性組
成物の硬化方法。4. A photocurable composition characterized by being subjected to a heat treatment and / or an active energy ray irradiation treatment after application using the photocurable composition according to claim 1. Curing method.
JP2000321110A 2000-10-20 2000-10-20 Photocurable composition and its curing method Pending JP2002128815A (en)

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CN01136436XA CN1216950C (en) 2000-10-20 2001-10-17 Photo-curing composition and its curing method
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