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JPS6178806A - Thermosetting acrylic resin composition for coating - Google Patents

Thermosetting acrylic resin composition for coating

Info

Publication number
JPS6178806A
JPS6178806A JP59199776A JP19977684A JPS6178806A JP S6178806 A JPS6178806 A JP S6178806A JP 59199776 A JP59199776 A JP 59199776A JP 19977684 A JP19977684 A JP 19977684A JP S6178806 A JPS6178806 A JP S6178806A
Authority
JP
Japan
Prior art keywords
group
weight
groups
formulas
compound
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.)
Granted
Application number
JP59199776A
Other languages
Japanese (ja)
Other versions
JPH0446306B2 (en
Inventor
Masuhito Ogushi
大串 益人
Tsutomu Asaha
浅葉 勉
Hiroshi Otsuka
博 大塚
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.)
JNC Corp
Original Assignee
Chisso Corp
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 Chisso Corp filed Critical Chisso Corp
Priority to JP59199776A priority Critical patent/JPS6178806A/en
Publication of JPS6178806A publication Critical patent/JPS6178806A/en
Publication of JPH0446306B2 publication Critical patent/JPH0446306B2/ja
Granted legal-status Critical Current

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  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Paints Or Removers (AREA)

Abstract

PURPOSE:The titled composition excellent in adhesion and stain resistance of film, obtained by radical-copolymerizing specified two (meth)acrylate esters, a vinyl group-containing polysiloxane and a vinyl group-containing silane compound. CONSTITUTION:The titled resin composition of a weight-average MW of 5,000-300,000 is obtained by radical-copolymerizing 50-80wt% 1-12C ester group-containing (meth)acrylate [e.g., methyl (meth)acrylate] with 20-5wt% OH group- or epoxy group-containing (meth)acrylate [e.g., 2-hydroxyethyl (meth) acrylate], 20-0.01wt% vinyl group-containing polysiloxane such as a vinyl group-terminated polyalkylsiloxane of v=2-100,000cP (at 25 deg.C) of the formula (wherein n is a positive integer) and 20-2wt% vinyl group-containing silane compound (e.g., vinyltrimethoxysilane) until the viscosity at 25 deg.C in a xylene solvent at a resin content of 40wt% has reached 100-2,000.

Description

【発明の詳細な説明】 本発明は、被覆用アクリル樹脂組成物に関する。ざらに
詳しくは、本発明は、特定種類および組成のアクリル酸
エステル若しくはメタアクリル酸エステル、ビニル基含
有ポリシロキサンおよびビニル基含有シラン化合物を共
重合せしめてなる該組成物に関する。 公知の熱硬化性
アクリル樹脂組成物は、種々の無機材料の塗材として、
光沢性、透明性、硬度、#候性および耐薬品性其他の 
  ゛すぐれた塗膜が得られるので広く用いられている
。しかしながら、該組成物に係る塗膜は、無機材料との
密着性が不十分である他、耐熱水性、耐アルカリ性の点
でも改良を必要としており、更に、油汚れを拭きとった
後シミが残り易い、粘着テープが剥がしにくく跡が残り
易い等多くの欠点も有している。
DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an acrylic resin composition for coating. More specifically, the present invention relates to a composition formed by copolymerizing an acrylic ester or methacrylic ester of a specific type and composition, a vinyl group-containing polysiloxane, and a vinyl group-containing silane compound. Known thermosetting acrylic resin compositions can be used as coating materials for various inorganic materials.
Gloss, transparency, hardness, weatherability, chemical resistance, etc.
``It is widely used because it provides an excellent coating film. However, the coating film based on this composition has insufficient adhesion to inorganic materials, requires improvement in terms of hot water resistance and alkali resistance, and also leaves stains after wiping off oil stains. It also has many drawbacks, such as being easy to remove, and the adhesive tape being difficult to remove and leaving marks.

本発明者等は、これらの欠点を改良し、表面の平滑な無
機材料の塗材として塗装後の密着性、耐汚染性のすぐれ
た熱硬化性アクリル樹脂組成物を見出すべく鋭意研究を
行った。その結果、a、特定のアルキル基炭素数を有す
るアクリル酸アルキル若しくはメタアクリル酸アルキル
、b、水酸基またはエポキシ基を有するアクリル酸エス
テル、C,ビニル基を有するポリシロキサンおよびd、
ビニル基含有シラン化合物のそれぞれ所定割合をラジカ
ル共重合せしめてなる共重合体組成物が上記目的に適合
することを見出して本発明を完成した。
The present inventors conducted intensive research to improve these drawbacks and find a thermosetting acrylic resin composition that has excellent adhesion and stain resistance after painting as a coating material for inorganic materials with a smooth surface. . As a result, a, an alkyl acrylate or an alkyl methacrylate having a specific alkyl group carbon number, b, an acrylate ester having a hydroxyl group or an epoxy group, C, a polysiloxane having a vinyl group, and d,
The present invention was completed by discovering that a copolymer composition obtained by radically copolymerizing predetermined proportions of vinyl group-containing silane compounds is suitable for the above purpose.

本発明は下記(1)の主要構成と(2)ないしく5)の
実施態様的構成を有する。
The present invention has the following main configurations (1) and embodiment configurations (2) to 5).

(1)下記a〜dの種類及び組成の単量体をラジカル共
重合せしめてなる被覆用熱硬化性アクリル樹脂組成物。
(1) A thermosetting acrylic resin composition for coating formed by radical copolymerization of monomers having the following types and compositions a to d.

a)エステル基の炭素数が1−12のアクリル酸エステ
ル若しくはエステル基の炭素数が1〜12のメタアクリ
ル酸エステルから選ばれた一以上の化合物50〜80重
量% b)水酸基またはエポキシ基を有するアクリル酸エステ
ル若しくは水酸基またはエポキシ基を有するメタアクリ
ル酸エステルから選ばれた一以上の化合物20〜5重量
% C)ビニル基を含有するポリシロキサン20〜0.01
ffi量% d)ビニル基を含有するシラン化合物20〜2重量%(
2)炭素数3以上の有機酸を0.1〜5重量%配合して
なる前記第(1)項に記載の組成物。
a) 50 to 80% by weight of one or more compounds selected from acrylic esters in which the ester group has 1 to 12 carbon atoms or methacrylic esters in which the ester group has 1 to 12 carbon atoms; b) hydroxyl group or epoxy group; 20 to 5% by weight of one or more compounds selected from acrylic esters having a hydroxyl group or methacrylic esters having a hydroxyl group or an epoxy group C) Polysiloxane containing a vinyl group 20 to 0.01%
ffi amount% d) 20 to 2% by weight of silane compound containing vinyl groups (
2) The composition according to item (1) above, which contains 0.1 to 5% by weight of an organic acid having 3 or more carbon atoms.

(3)ラジカル共重合せしめて得られた共重合体の重量
平均分子量が5,000ないし300,000である前
記第(1)項に記載の組成物。
(3) The composition according to item (1) above, wherein the copolymer obtained by radical copolymerization has a weight average molecular weight of 5,000 to 300,000.

(4)有機酸がアクリル酸若しくは無水マレイン酸であ
る前記第(2)項に記載の組成物。
(4) The composition according to item (2) above, wherein the organic acid is acrylic acid or maleic anhydride.

(5)ビニル基を含有したポリシロキサンが、下記e〜
hの種類、構造式および粘度を有する単量体から選ばれ
た一以上の化合物である前記第(1)項に記載の組成物
(5) The vinyl group-containing polysiloxane is
The composition according to item (1) above, which is one or more compounds selected from monomers having the type, structural formula, and viscosity of h.

e 、 末端にビニル基を有するポリアルキルシロキサ
ンで η=2〜100000センチポイズ(25℃)の化合物
(構造式下記、たX(、nは正の整数)f、ポリジメチ
ル−ポリメチルビニルシロキサンコポリマーで η=10〜100000センチポイズ(25℃)の化合
物(構造式下記、た(1.m、nは正の整数)g、末端
にメタクリロシプロビル基を有するポリジメチルシロキ
サンで η=5〜toooooセンチポイズ(25℃)の化合物
(構造式下記、たffLnは正の整数)h、ポリジメチ
ル−メタアクリロキシプロピルメチルシロキサンで η=10〜100000センチボイズ(25℃)の化合
物(構造式下記、たCしnは正の整数) Hs およびeないしhにおいて5i−CH3基の一部をフェ
ニル基に変換したもの。
e, a polyalkylsiloxane having a vinyl group at the end and a compound with η = 2 to 100,000 centipoise (25°C) (the structural formula is as follows, A compound with η = 10 to 100,000 centipoise (at 25°C) (the structural formula is as follows: (25℃) compound (with the structural formula below, ffLn is a positive integer) h, a polydimethyl-methacryloxypropylmethylsiloxane compound with η = 10 to 100,000 centivoise (25℃) (with the structural formula below, ffLn is a positive integer) (n is a positive integer) Hs and a part of the 5i-CH3 group in e to h is converted to a phenyl group.

本発明の構成と効果につき以下に詳述する。The configuration and effects of the present invention will be explained in detail below.

本発明の組成物は、下記a −dの4群の単量体   
 (をラジカル共重合せしめることにより得られる。
The composition of the present invention comprises monomers of the following four groups a to d.
(obtained by radical copolymerization of

a群の化合物としては、エステル基の炭素数が1−12
のアクリル酸エステル若しくはエステル基の炭素数がl
〜12のメタクリル酸エステルを全単量体の50〜80
重量%使用する。具体例としては、エチルアクリレート
若しくはブチルアクリレートのようなアクリレートまた
は、メチルメタアクリレート、エチルメタアクリレート
若しくはブチルメタアクリレートが挙げられる。これら
のアクリレート若しくはメタアクリレートのアルキル基
の炭素数が13以上では、最終製品についての塗材とし
ての物性が不十分となる。また使用iJ囲が50重量%
未満および80重量%を超える場合も同様である。
For compounds of group a, the ester group has 1 to 12 carbon atoms.
The number of carbon atoms in the acrylic ester or ester group is l
~12 methacrylic acid esters account for 50 to 80 of the total monomers
Use % by weight. Specific examples include acrylates such as ethyl acrylate or butyl acrylate, or methyl methacrylate, ethyl methacrylate or butyl methacrylate. If the alkyl group of these acrylates or methacrylates has 13 or more carbon atoms, the physical properties of the final product as a coating material will be insufficient. Also, the used iJ area is 50% by weight.
The same applies to cases where the amount is less than 80% by weight and more than 80% by weight.

次にb群の化合物としては水酸基またはエポキシ基を有
するアクリル酸エステル若しくは水酸基またはエポキシ
基を有するメタアクリル酸エステルを全単量体の20〜
5重量%使用する。これらの具体例として2−ヒドロキ
シエチルアクリレート。
Next, as a compound of group b, an acrylic ester having a hydroxyl group or an epoxy group, or a methacrylic ester having a hydroxyl group or an epoxy group is used.
Use 5% by weight. A specific example of these is 2-hydroxyethyl acrylate.

2−ヒドロキシエチルメタアクリレートおよびグリシジ
ルメタアクリレートが挙げられる。b群の化合物の使用
割合が、20重量%を超えると最終!ll動物用いて製
造した塗膜の物性が不良となるおそれが生じ、5重量%
未満では、最終組成物の硬化性が不十分である。
Mention may be made of 2-hydroxyethyl methacrylate and glycidyl methacrylate. If the proportion of the compound in group b exceeds 20% by weight, the final! ll There is a risk that the physical properties of the coating film produced using animals may deteriorate, and 5% by weight
If it is less than that, the curing properties of the final composition will be insufficient.

次に、0群の化合物としては、ビニル基を含有するポリ
シロキサンを全単量体の20〜0.01重量%使用する
。ビニル基は、該ポリシロキサンの末端基として結合し
ていてもよく、シロキサン繰返し単位におけるSiに直
接にまたは他の官能基を介して結合していてもよい、該
ポリシロキサンの使用割合が20重量%を超えると塗膜
が軟らかすぎさらに密着性がとぼしくなり、0.01重
量%未満では耐汚染性、非粘着性等塗膜の物性が不十分
である。
Next, as the compound of group 0, polysiloxane containing a vinyl group is used in an amount of 20 to 0.01% by weight based on the total monomers. The vinyl group may be bonded as a terminal group of the polysiloxane, or may be bonded directly to Si in the siloxane repeating unit or via another functional group, when the proportion of the polysiloxane used is 20% by weight. If it exceeds 0.01% by weight, the coating film will be too soft and the adhesion will be poor; if it is less than 0.01% by weight, the physical properties of the coating film, such as stain resistance and non-adhesiveness, will be insufficient.

該ポリシロキサンの具体例としては、前述(5)のeな
いしhの化合物があげられる。これらの化合物のηにつ
いてそれぞれ前述の数値範囲のものが好ましく使用でき
る。
Specific examples of the polysiloxane include the compounds e to h described in (5) above. Those compounds having η in the above-mentioned numerical ranges can be preferably used.

最後にd群の化合物としては、ビニル基を含有するシラ
ン化合物を全単量体の20〜2重量%使用する。シラン
化合物であるから、前述のビニル基以外に珪素原子に直
結した加水分解性の官能基を2個または3個有する。そ
れらの官能基は限定されないが、炭素alないし4のア
ルコキシル基が使用し易く、かつ、好ましい結果が得ら
れる。このようなビニル基を含有するシラン化合物の具
体例としては、ビニルトリメトキシシラン、ビニルトリ
エトキシシラン、ビニルトリメトキシエトキシシラン、
メチルビニルジメトキシシラン、メチルビニルジェトキ
シシラン、γ−メタシクロキシプロピルトリメトキシシ
ランおよびγ−メタシクロキシプロピルメチルジメトキ
シシランがあげられる。
Finally, as the compound of group d, a silane compound containing a vinyl group is used in an amount of 20 to 2% by weight based on the total monomers. Since it is a silane compound, it has two or three hydrolyzable functional groups directly bonded to a silicon atom in addition to the above-mentioned vinyl group. Although these functional groups are not limited, alkoxyl groups having 4 carbons are easy to use and preferable results can be obtained. Specific examples of such silane compounds containing vinyl groups include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxyethoxysilane,
Examples include methylvinyldimethoxysilane, methylvinyljethoxysilane, γ-metacycloxypropyltrimethoxysilane and γ-metacycloxypropylmethyldimethoxysilane.

以上のaないしd群の単量体は、ラジカル発生剤の存在
下に共重合せしめる。共重合の形式は限定されないが、
溶剤の存在下の溶剤重合が実施し易く好ましい結果が得
られる。か−る溶剤としては例えば、トルエン若しくは
キシレンのような芳香族炭水素、メチルエチルケトン若
しくはアセトンのようなケトン類、n−ブタノール若し
くはシクロヘキサノールのようなアルコール類を挙げる
ことができる。ラジカル発生剤の種類および使用割合は
、通常のアクリル酸エステルまたはメタアクリル酸エス
テルの重合に使用する場合と同様である。すなわち、例
えば過酸化ベンゾイル若しくはアゾビスイソブチロジニ
トリルのような該発生剤を単量体の0.2〜2重量%使
用し、核剤の半減期に応じ温度80−120℃で、前記
共重合を行う。該共重合において、4群の単量体は全量
を一時に混合して共重合に供してもよく、単量体混合物
の一部を共重合中に他の単量体若しくは単量体混合物を
追加補給してもよい。
The above monomers of groups a to d are copolymerized in the presence of a radical generator. Although the form of copolymerization is not limited,
Solvent polymerization in the presence of a solvent is easy to carry out and provides favorable results. Examples of such solvents include aromatic hydrocarbons such as toluene or xylene, ketones such as methyl ethyl ketone or acetone, and alcohols such as n-butanol or cyclohexanol. The type and proportion of the radical generator used are the same as those used in ordinary polymerization of acrylic esters or methacrylic esters. That is, using 0.2 to 2% by weight of the generator, such as benzoyl peroxide or azobisisobutyrodinitrile, based on the monomer, and at a temperature of 80-120° C., depending on the half-life of the nucleating agent. Carry out polymerization. In this copolymerization, all of the monomers of the 4 groups may be mixed at once and subjected to copolymerization, or a part of the monomer mixture may be added to other monomers or monomer mixtures during copolymerization. Additional supplies may be provided.

本発明に係るアクリル樹脂組成物の重合の程度は、キシ
レン溶媒、樹脂分40重量%における25℃の粘度で1
00ないし2000、好ましくは150ないし1000
とすることが好ましい0重合度の調節は、ラジカル発生
剤若しくは連鎖移動剤の使用量によって行うことは、通
常のアクリル樹脂製造の場合と同様である。上述の粘度
が100未満では未重合の単量体が残存し易く、該共合
体組成物の粘度が低すぎるため、塗材としての作業性も
良好とはいえない。反対に該粘度が2000を超える場
合、該粘度が高すぎるため該作業性が不良となるのみな
らず、塗装後の塗膜の耐熱水性が低下する傾向を生じる
The degree of polymerization of the acrylic resin composition according to the present invention is 1 at a viscosity of 1 at 25°C in a xylene solvent and a resin content of 40% by weight.
00 to 2000, preferably 150 to 1000
Adjustment of the degree of polymerization, which is preferably 0, is carried out by adjusting the amount of the radical generator or chain transfer agent used, as in the case of ordinary acrylic resin production. When the above-mentioned viscosity is less than 100, unpolymerized monomers tend to remain, and the viscosity of the copolymer composition is too low, so that the workability as a coating material cannot be said to be good. On the other hand, if the viscosity exceeds 2,000, the viscosity is too high, resulting in not only poor workability but also a tendency for the hot water resistance of the coated film to decrease.

以上のようにして、本発明に係る被覆用熱硬化性アクリ
ル樹脂組成物である共重合体が得られる。共重合の際使
用した溶剤は、そのま−含有させておいてもよく、減圧
加熱等して未反応の前述a〜dの単量体と共に回収して
もよい。
In the manner described above, a copolymer which is a thermosetting acrylic resin composition for coating according to the present invention is obtained. The solvent used in the copolymerization may be contained as is, or may be recovered together with the unreacted monomers a to d by heating under reduced pressure.

本発明に係るアクリル樹脂組成物は、前述のグループb
の単量体が含有している官能基を利用して架橋反応させ
、熱硬化させることができる。そのための反応促進剤と
して下記のような有機酸若しくは有機塩基化合物を該ア
クリル樹脂組成物に対して、0.1〜5重量%好ましく
は0.5〜3重量%使用する。
The acrylic resin composition according to the present invention has the above-mentioned group b.
It is possible to carry out a crosslinking reaction using the functional groups contained in the monomers and to thermally cure them. As a reaction accelerator for this purpose, the following organic acid or organic base compound is used in an amount of 0.1 to 5% by weight, preferably 0.5 to 3% by weight, based on the acrylic resin composition.

か覧る有機酸の具体例としては、アクリル酸。A specific example of an organic acid that can be seen is acrylic acid.

メタクリル酸、フタル酸、マレイン酸若しくはp−トル
エンスルホン酸を挙げることができる。アクリル酸若し
くはメタクリル酸は、本発明に係るアクリル樹脂組成物
製造のための共重合時に添加して同時に共重合させる使
用方法が可能である。他の有機酸は、該組成物製造後に
添加される。
Mention may be made of methacrylic acid, phthalic acid, maleic acid or p-toluenesulfonic acid. Acrylic acid or methacrylic acid can be added during copolymerization for producing the acrylic resin composition according to the present invention, and copolymerized at the same time. Other organic acids are added after the composition is prepared.

上述の有機塩、基化合物としては、前述のb群の化合物
に係るエポキシ基開環触媒として用いられるベンジルジ
メチルアミン、ポリアミン若しくはポリアミドを挙げる
ことができる。しかしながら、次のアミノ基含有シラン
化合物1例えばγ−アミノプロピルトリエトキシシラン
、  3−(2−7ミノエチル)アミノプロピルトリメ
トキシシラン若しくは3−(2−7ミノエチル)アミノ
プロピルメチルジメトキシシランは、さらに好ましく使
用できる。これらの有機塩基化合物は、本発明に係るア
クリル樹脂組成物製造後に添加混合する。
Examples of the above-mentioned organic salts and base compounds include benzyldimethylamine, polyamines, and polyamides used as epoxy group ring-opening catalysts for the above-mentioned group b compounds. However, the following amino group-containing silane compounds 1 such as γ-aminopropyltriethoxysilane, 3-(2-7minoethyl)aminopropyltrimethoxysilane or 3-(2-7minoethyl)aminopropylmethyldimethoxysilane are more preferred. Can be used. These organic basic compounds are added and mixed after producing the acrylic resin composition according to the present invention.

本発明の組成物を塗料として使用するに際しては、同種
の塗料に配合される各種の助剤例えば有機若しくは無機
顔料、染料、紫外線吸収剤1分散剤、硬化促進剤若しく
はたれ防止剤を使用できる。その他、塗装上の作業性若
しくは仕上り性。
When using the composition of the present invention as a paint, various auxiliary agents that are included in paints of the same type, such as organic or inorganic pigments, dyes, ultraviolet absorbers, dispersants, curing accelerators, or anti-sagging agents can be used. In addition, the workability or finish quality of painting.

保存安定性を改善するために溶剤例えばキシレン、酢酸
ブチル、エチルセロソルブ若しくはブタノールを適量配
合することができる。
In order to improve storage stability, a suitable amount of a solvent such as xylene, butyl acetate, ethyl cellosolve or butanol can be incorporated.

以上のように調整された本発明の組成物に係る塗料を無
機材料表面に塗布する方法は、常用の例エバ、カーテン
フローコート、ロールコート、スプレー若しくはディッ
ピング法のいづれも採用できる。
As a method for applying the paint according to the composition of the present invention prepared as described above onto the surface of an inorganic material, any of the commonly used methods such as coating, curtain flow coating, roll coating, spraying, or dipping can be employed.

本発明品は、熱硬化性シリコン変性アクリル樹脂組成物
であり、塗膜形成後の加熱によって硬化させる。加熱温
度は150〜280℃好ましくは200〜270℃で、
1分ないし30分好ましくは3分ないし15分のような
短時間で硬化する。他の硬化方法としては次の低温硬化
がある。
The product of the present invention is a thermosetting silicone-modified acrylic resin composition, and is cured by heating after the coating film is formed. The heating temperature is 150-280°C, preferably 200-270°C,
It cures in a short time such as 1 minute to 30 minutes, preferably 3 minutes to 15 minutes. Other curing methods include the following low temperature curing.

本発明の組成物に係る塗料は、反応促進剤である有機酸
を含有し、室温ないし80℃のような低温でも架橋反応
が徐々に進行して硬化するので、か−る低温硬化法は例
えば、木工用、プラスチック用等に利用できる。
The paint according to the composition of the present invention contains an organic acid as a reaction accelerator, and the crosslinking reaction gradually progresses and cures even at low temperatures such as room temperature to 80°C. It can be used for woodworking, plastics, etc.

本発明に係るアクリル樹脂組成物は、塗料として使用し
た際、架橋度の高い密着性、耐汚染性等のすぐれた塗膜
が得られる。この理由は、次の三点にあると推察される
。すなわち、■アクリル樹脂組成物の原料であるアクリ
ル酸エステル若しくはメタアクリル酸エステル類ならび
にビニル基含有ポリシロキサ/の配合比および、該組成
物共重合体の重合度が最終的に塗膜の柔軟性と硬度を適
切に維持し、緻密な膜面を形成しうること、またこの時
、ビニル基含有ポリシロキサンが骨格に組込まれるため
、通常のシリコーンオイルの添加の場合と違ってブリー
ドが極くわずかであること、■共重合成分であるビニル
基含有シラン化合物が、シロキサン結合、水酸基との結
合、被塗布物である無機材料との化学的若しくは物理的
結合を構成すること、および■該組成物に添加された有
amが、架橋反応を促進することである。
When the acrylic resin composition according to the present invention is used as a coating material, a coating film with a high degree of crosslinking and excellent adhesion and stain resistance can be obtained. The reason for this is presumed to be the following three points. That is, (1) the blending ratio of acrylic esters or methacrylic esters and vinyl group-containing polysiloxane, which are the raw materials of the acrylic resin composition, and the degree of polymerization of the composition copolymer ultimately determine the flexibility of the coating film. It is possible to maintain appropriate hardness and form a dense film surface, and at this time, because the vinyl group-containing polysiloxane is incorporated into the skeleton, there is very little bleeding, unlike when adding ordinary silicone oil. (1) The vinyl group-containing silane compound as a copolymerization component forms a siloxane bond, a bond with a hydroxyl group, and a chemical or physical bond with the inorganic material to be coated, and (2) the composition has The added am is to promote the crosslinking reaction.

以下、合成例および実施例(使用例)により本発明を説
明する。
The present invention will be explained below with reference to synthesis examples and examples (examples of use).

合成例1 メタアクリル酸メチル50重量部(以下同じ)と   
 1メタアクリル酸ブチル10部、グリシジルメタアク
リレート20部、アクリル酸2部、末端ビニルボリジメ
チルシロキナン(η−50)10部、γ−メタシクロキ
シグロビルトリメトキシシランlO部をキシレン 15
0部に溶解し、過酸化ベンゾイル1部を加え、窒素気流
’F too℃、4時間反応し、表1に示す粘度(25
℃)21Oセンチボイズのシリコーン変性アクリル重合
体を得た。
Synthesis Example 1 50 parts by weight of methyl methacrylate (same below)
1 10 parts of butyl methacrylate, 20 parts of glycidyl methacrylate, 2 parts of acrylic acid, 10 parts of terminal vinyl borodimethylsilokinane (η-50), 10 parts of γ-metacycloxyglobyl trimethoxysilane, 15 parts of xylene
0 parts, added 1 part of benzoyl peroxide, reacted for 4 hours under a nitrogen stream at 'F toooC, and the viscosity shown in Table 1 (25
℃) A silicone-modified acrylic polymer having a diameter of 210 cm was obtained.

合成例2〜6 成分及び組成を変え、合成例1と同様な反応を行って表
1に示す粘度(25℃)のシリコーン変性アクリル重合
体を得た。
Synthesis Examples 2 to 6 The same reactions as in Synthesis Example 1 were carried out with different components and compositions to obtain silicone-modified acrylic polymers having the viscosities (25°C) shown in Table 1.

実施例1〜4及び比較例1〜2 合成例1〜6で得た重合体を当型量のキシレン−ブタノ
ール(2:1)の混合溶媒で希釈し、普通ガラス板(J
IS R321)に塗布230℃、5分間の加熱硬化を
行って約10JLの塗膜を得、評価した。その結果を表
2に示す。
Examples 1 to 4 and Comparative Examples 1 to 2 The polymers obtained in Synthesis Examples 1 to 6 were diluted with an equivalent amount of a mixed solvent of xylene-butanol (2:1), and a common glass plate (J
IS R321) and heat-cured at 230° C. for 5 minutes to obtain a coating film of about 10 JL, which was evaluated. The results are shown in Table 2.

なお、評価は次の方法によって行なった。In addition, the evaluation was performed by the following method.

判 定:O全く変化のないもの Δ わずかに割れ、白化等変化のあったもの × 明らかに割れ、白化等変化のあったもの 鉛筆硬度: JIS K 5400に準拠密着性:基盤
目剥離テス) (1mm巾にカッターで100個のマス
目を作り、セロファンテープで5回剥離テストを実施し
て、剥離せずに残ったマス目の個数を平均する) #を熱水性:蓋のある沸騰水容器に2時間浸a後、判定
する。
Judgment: O No change at all Δ Slight cracking, whitening, etc. changes × Obviously cracking, whitening, etc. changes Pencil hardness: Compliant with JIS K 5400 Adhesion: Base grain peeling test) Make 100 squares 1 mm wide with a cutter, perform a peeling test with cellophane tape 5 times, and average the number of squares that remain without peeling.) # is hydrothermal: boiling water with a lid. Judgment is made after soaking in the container for 2 hours.

熱水後密着性:基盤目をつけたテストピースを沸騰水に
2時間浸漬し、基盤目剥離 テストをする。
Adhesion after hot water: A test piece with a base grain attached is immersed in boiling water for 2 hours, and a base grain peeling test is performed.

耐アルカリ性:WA度1重量%の水酸化ナトリウム水溶
液に室温にて5時間浸漬後、 判定する。
Alkali resistance: Determined after 5 hours of immersion in a sodium hydroxide aqueous solution with a WA degree of 1% by weight at room temperature.

耐汚染性:マジックインキでマーキングし、 30分放
置後トルエンを用いて拭きとり、判 定する。
Stain resistance: Mark with marker ink, leave for 30 minutes, then wipe off with toluene and judge.

非粘着性:セロファンテープの剥がし易さで判定する。Non-adhesiveness: Judged by the ease of peeling off the cellophane tape.

表1 註 MMA・   メタアクリフ4メチルBMA : 
  メタアクジノ4動−ブチル島 −アクリノ漕エチル LMA :    メタアクリノ漕ラウリルGNA: 
   グリシジルメタアクリレート1(EMA:2−ヒ
ドロキシエチルメタアクリレートヒニルポリシロキサン
:末端ビニルポリジメチルシロキサン(η=50)メタ
クリルポリシロキサン:末端メタクリロキシプロピルポ
リジメチルシロキサン(η−200)lclpS−に:
 メタクリロキシプロピルトリメトキシシランVTS−
に: ビニルトリメトキシシラン表2
Table 1 Note: MMA/Metaacrif 4-methyl BMA:
Metaacryno-4-butyl island-Acryno-ethyl LMA: Meta-Acryno-Lauryl GNA:
Glycidyl methacrylate 1 (EMA: 2-hydroxyethyl methacrylate hinyl polysiloxane: terminal vinyl polydimethylsiloxane (η=50) methacryl polysiloxane: terminal methacryloxypropyl polydimethylsiloxane (η-200) lclpS-:
Methacryloxypropyltrimethoxysilane VTS-
In: Vinyltrimethoxysilane Table 2

Claims (1)

【特許請求の範囲】 (1)下記a〜dの種類及び組成の単量体をラジカル共
重合せしめてなる被覆用熱硬化性アクリル樹脂組成物。 a)エステル基の炭素数が1〜12のアクリル酸エステ
ル若しくはエステル基の炭素数が1〜12のメタアクリ
ル酸エステルから選ばれた一以上の化合物50〜80重
量% b)水酸基またはエポキシ基を有するアクリル酸エステ
ル若しくは水酸基またはエポキシ基を有するメタアクリ
ル酸エステルから選ばれた一以上の化合物20〜5重量
% c)ビニル基を含有するポリシロキサン20〜0.01
重量% d)ビニル基を含有するシラン化合物20〜2重量%(
2)炭素数3以上の有機酸を0.1〜5重量%配合して
なる特許請求の範囲第(1)項に記載の組成物。 (3)ラジカル共重合せしめて得られた共重合体の重量
平均分子量が5,000ないし300,000である特
許請求の範囲第(1)項に記載の組成物。 (4)有機酸がアクリル酸若しくは無水マレイン酸であ
る特許請求の範囲第(2)項に記載の組成物。 (5)ビニル基を含有したポリシロキサンが、下記e〜
hの種類、構造式および粘度を有する単量体から選ばれ
た一以上の化合物である特許請求の範囲第(1)項に記
載の組成物。 e、末端にビニル基を有するポリアルキルシロキサンで η=2〜100000センチポイズ(25℃)の化合物
(構造式下記、たゞしnは正の整数) ▲数式、化学式、表等があります▼ f、ポリジメチル−ポリメチルビニルシロキサンコポリ
マーで η=10〜100000センチポイズ(25℃)の化合
物(構造式下記、たゞしm、nは正の整数) ▲数式、化学式、表等があります▼ g、末端にメタクリロシプロピル基を有するポリジメチ
ルシロキサンで η=5〜100000センチポイズ(25℃)の化合物
(構造式下記、たゞしnは正の整数) ▲数式、化学式、表等があります▼▲数式、化学式、表
等があります▼ h、ポリジメチル−メタアクリロキシプロピルメチルシ
ロキサンで η=10〜100000センチポイズ(25℃)の化合
物(構造式下記、たゞしnは正の整数) ▲数式、化学式、表等があります▼ およびeないしhにおいてSi−CH_3基の一部をフ
ェニル基に変換したもの。
[Scope of Claims] (1) A thermosetting acrylic resin composition for coating made by radical copolymerization of monomers having the following types and compositions a to d. a) 50 to 80% by weight of one or more compounds selected from acrylic esters in which the ester group has 1 to 12 carbon atoms or methacrylic esters in which the ester group has 1 to 12 carbon atoms; b) hydroxyl group or epoxy group; 20 to 5% by weight of one or more compounds selected from acrylic esters having hydroxyl groups or methacrylic esters having hydroxyl groups or epoxy groups c) Polysiloxane containing vinyl groups 20 to 0.01%
Weight% d) 20-2% by weight of silane compound containing vinyl groups (
2) The composition according to claim (1), which contains 0.1 to 5% by weight of an organic acid having 3 or more carbon atoms. (3) The composition according to claim (1), wherein the copolymer obtained by radical copolymerization has a weight average molecular weight of 5,000 to 300,000. (4) The composition according to claim (2), wherein the organic acid is acrylic acid or maleic anhydride. (5) The vinyl group-containing polysiloxane is
The composition according to claim (1), which is one or more compounds selected from monomers having the type, structural formula, and viscosity of h. e, a compound of polyalkylsiloxane with a vinyl group at the end and η = 2 to 100,000 centipoise (at 25°C) (the structural formula is shown below, where n is a positive integer) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ f, Polydimethyl-polymethylvinylsiloxane copolymer compound with η = 10 to 100,000 centipoise (25℃) (Structural formula below, where m and n are positive integers) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ g, terminal A compound of polydimethylsiloxane with methacrylocypropyl group and η = 5 to 100,000 centipoise (25℃) (Structural formula below, where n is a positive integer) ▲There are mathematical formulas, chemical formulas, tables, etc.▼▲Mathematical formulas, There are chemical formulas, tables, etc. ▼ h, polydimethyl-methacryloxypropylmethylsiloxane compound with η = 10 to 100,000 centipoise (25°C) (Structural formula below, where n is a positive integer) ▲ Numerical formulas, chemical formulas, There are tables etc. ▼ And in e to h, some of the Si-CH_3 groups are converted to phenyl groups.
JP59199776A 1984-09-25 1984-09-25 Thermosetting acrylic resin composition for coating Granted JPS6178806A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP59199776A JPS6178806A (en) 1984-09-25 1984-09-25 Thermosetting acrylic resin composition for coating

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP59199776A JPS6178806A (en) 1984-09-25 1984-09-25 Thermosetting acrylic resin composition for coating

Publications (2)

Publication Number Publication Date
JPS6178806A true JPS6178806A (en) 1986-04-22
JPH0446306B2 JPH0446306B2 (en) 1992-07-29

Family

ID=16413421

Family Applications (1)

Application Number Title Priority Date Filing Date
JP59199776A Granted JPS6178806A (en) 1984-09-25 1984-09-25 Thermosetting acrylic resin composition for coating

Country Status (1)

Country Link
JP (1) JPS6178806A (en)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01131254A (en) * 1987-08-14 1989-05-24 Mitsubishi Kasei Vinyl Co Molded vinyl chloride based resin product
JPH01184130A (en) * 1988-01-18 1989-07-21 Mitsubishi Kasei Vinyl Co Agricultural vinyl chloride resin film
JPH01206040A (en) * 1987-10-08 1989-08-18 Mitsubishi Kasei Vinyl Co Vinyl chloride resin film for agriculture
JPH02108536A (en) * 1988-10-18 1990-04-20 Mitsubishi Kasei Vinyl Co Vinyl chloride resin film for agricultural use
JPH02113939A (en) * 1988-10-24 1990-04-26 Mitsubishi Kasei Vinyl Co Flexible vinyl chloride resin film for agriculture
JPH02233752A (en) * 1989-03-08 1990-09-17 Kansai Paint Co Ltd Curable composition
GB2247461A (en) * 1990-08-29 1992-03-04 Kansai Paint Co Ltd Polysiloxane and resin coating composition
WO2005032814A1 (en) * 2003-10-06 2005-04-14 Fuji Photo Film Co., Ltd. Hard coating article, curing composition, and information recording media
JP2005314606A (en) * 2004-04-30 2005-11-10 Kuraray Co Ltd Method for producing silicon-containing polymer and silicon-containing polymer
WO2012091178A1 (en) 2010-12-28 2012-07-05 Dow Corning Toray Co., Ltd. Additive for a coating agent and coating agent containing same
CN102898578A (en) * 2012-07-16 2013-01-30 杭州师范大学 Self-crosslinking silicone-acrylate copolymer emulsion and preparation method
CN107075122A (en) * 2014-12-16 2017-08-18 湛新奥地利有限公司 Flow ability modifying agent for coating composition

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4831252A (en) * 1971-08-26 1973-04-24
JPS5142752A (en) * 1974-10-09 1976-04-12 Japan Atomic Energy Res Inst KOKASEIJUSHISOSEIBUTSU
JPS5462299A (en) * 1977-10-26 1979-05-19 Japan Atom Energy Res Inst Curable resin composition
JPS5947216A (en) * 1982-09-13 1984-03-16 Shin Etsu Chem Co Ltd Primer composition

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4831252A (en) * 1971-08-26 1973-04-24
JPS5142752A (en) * 1974-10-09 1976-04-12 Japan Atomic Energy Res Inst KOKASEIJUSHISOSEIBUTSU
JPS5462299A (en) * 1977-10-26 1979-05-19 Japan Atom Energy Res Inst Curable resin composition
JPS5947216A (en) * 1982-09-13 1984-03-16 Shin Etsu Chem Co Ltd Primer composition

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01131254A (en) * 1987-08-14 1989-05-24 Mitsubishi Kasei Vinyl Co Molded vinyl chloride based resin product
JPH0575008B2 (en) * 1987-08-14 1993-10-19 Mitsubishi Kasei Vinyl
JPH0566869B2 (en) * 1987-10-08 1993-09-22 Mitsubishi Kasei Vinyl
JPH01206040A (en) * 1987-10-08 1989-08-18 Mitsubishi Kasei Vinyl Co Vinyl chloride resin film for agriculture
JPH01184130A (en) * 1988-01-18 1989-07-21 Mitsubishi Kasei Vinyl Co Agricultural vinyl chloride resin film
JPH0566868B2 (en) * 1988-01-18 1993-09-22 Mitsubishi Kasei Vinyl
JPH02108536A (en) * 1988-10-18 1990-04-20 Mitsubishi Kasei Vinyl Co Vinyl chloride resin film for agricultural use
JPH0460823B2 (en) * 1988-10-18 1992-09-29 Mitsubishi Kasei Vinyl
JPH02113939A (en) * 1988-10-24 1990-04-26 Mitsubishi Kasei Vinyl Co Flexible vinyl chloride resin film for agriculture
JPH0460825B2 (en) * 1988-10-24 1992-09-29 Mitsubishi Kasei Vinyl
JPH02233752A (en) * 1989-03-08 1990-09-17 Kansai Paint Co Ltd Curable composition
GB2247461A (en) * 1990-08-29 1992-03-04 Kansai Paint Co Ltd Polysiloxane and resin coating composition
GB2247461B (en) * 1990-08-29 1994-07-06 Kansai Paint Co Ltd Curable resin composition and curing method
WO2005032814A1 (en) * 2003-10-06 2005-04-14 Fuji Photo Film Co., Ltd. Hard coating article, curing composition, and information recording media
JP2005314606A (en) * 2004-04-30 2005-11-10 Kuraray Co Ltd Method for producing silicon-containing polymer and silicon-containing polymer
JP4568017B2 (en) * 2004-04-30 2010-10-27 株式会社クラレ Method for producing silicon-containing polymer and silicon-containing polymer
WO2012091178A1 (en) 2010-12-28 2012-07-05 Dow Corning Toray Co., Ltd. Additive for a coating agent and coating agent containing same
CN102898578A (en) * 2012-07-16 2013-01-30 杭州师范大学 Self-crosslinking silicone-acrylate copolymer emulsion and preparation method
CN102898578B (en) * 2012-07-16 2015-01-07 杭州师范大学 Self-crosslinking silicone-acrylate copolymer emulsion and preparation method
CN107075122A (en) * 2014-12-16 2017-08-18 湛新奥地利有限公司 Flow ability modifying agent for coating composition
JP2018505233A (en) * 2014-12-16 2018-02-22 オールネックス オーストリア ゲーエムベーハー Fluidity improver for coating compositions

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