JPH07314615A - Thermoplastic resin laminate - Google Patents
Thermoplastic resin laminateInfo
- Publication number
- JPH07314615A JPH07314615A JP11001994A JP11001994A JPH07314615A JP H07314615 A JPH07314615 A JP H07314615A JP 11001994 A JP11001994 A JP 11001994A JP 11001994 A JP11001994 A JP 11001994A JP H07314615 A JPH07314615 A JP H07314615A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- thermoplastic resin
- matting
- monomer
- parts
- 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
Links
Landscapes
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は艶消し性に優れた熱可塑
性樹脂積層物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin laminate excellent in mattness.
【0002】[0002]
【従来の技術】アクリル樹脂、ポリカーボネート樹脂、
塩化ビニル樹脂、ABS樹脂などの熱可塑性樹脂から得
られる成形品は一般に艶を有しており、それが用途によ
っては重要な特性である場合がある。しかし、一方では
このような艶を必要としなかったり、むしろ艶がない方
が好まれる用途も多い。2. Description of the Related Art Acrylic resin, polycarbonate resin,
Molded articles obtained from thermoplastic resins such as vinyl chloride resin and ABS resin generally have luster, which may be an important characteristic depending on the application. On the other hand, on the other hand, there are many applications in which such luster is not necessary, or rather, luster is preferred.
【0003】従来の熱可塑性樹脂の艶消し方法は、大別
して(1)紋つけ加工、艶消し加工による方法と(2)
無機物又は有機物の艶消し剤を添加する方法に分けられ
る。(1)の方法は一般に物性の低下が少ないという利
点はあるものの生産性は悪く加工費がかさむ上、艶消し
効果も不十分であり、多くの場合二次加工を施す用途に
は不向きである。逆に(2)の方法は生産性がそれほど
低下せずに、艶消しの程度のコントロールも可能であ
り、二次加工を施す用途にも適用できるが、物性の低下
という大きな問題を含んでいる。特にシリカゲルなどの
無機物を艶消し剤として用いた場合には、耐衝撃性や強
伸度などの物性の低下が著しい。[0003] The conventional matting methods for thermoplastic resins are roughly classified into (1) a method by imprinting and matting, and (2)
It can be divided into the methods of adding an inorganic or organic matting agent. The method (1) generally has the advantage of less deterioration in physical properties, but has poor productivity and a high processing cost, and the matting effect is insufficient. In many cases, it is not suitable for secondary processing. . On the contrary, the method (2) can control the degree of matting without lowering the productivity so much and can be applied to the application of secondary processing, but it has a big problem of deterioration of physical properties. . In particular, when an inorganic material such as silica gel is used as a matting agent, the physical properties such as impact resistance and strength and elongation are significantly deteriorated.
【0004】一方、有機物特に高分子系の艶消し剤を用
いる方法が特開昭56−36535号公報に開示されて
いるが、その方法は懸濁重合することによって得られる
平均粒径35〜500μの架橋ポリマーを用いる方法で
ある。On the other hand, a method using an organic substance, especially a high-molecular matting agent is disclosed in JP-A-56-36535, which is an average particle size of 35 to 500 .mu.m obtained by suspension polymerization. This is a method using a cross-linked polymer.
【0005】[0005]
【発明が解決しようとする課題】しかしながら、上記の
高分子系の艶消し剤を使用する方法では、耐衝撃性や強
伸度の物性の低下は小さいが、艶消し効果は不十分であ
った。本発明はこれらの問題点を解決することを目的と
するものである。However, in the method using the above-mentioned high molecular weight matting agent, the physical properties such as impact resistance and strength / elongation are less deteriorated, but the matting effect is insufficient. . The present invention aims to solve these problems.
【0006】[0006]
【課題を解決するための手段】本発明者等は上記問題点
について鋭意検討した結果、(メタ)アクリル酸ヒドロ
キシアルキルエステル、メタクリル酸アルキルエステル
および特定の架橋性モノマーから得られる架橋ポリマー
を熱可塑性樹脂に配合した熱可塑性樹脂組成物を熱可塑
性樹脂の表面に積層させることにより、上記問題点を解
決し、本発明に到達した。Means for Solving the Problems As a result of intensive studies on the above problems, the present inventors have found that a crosslinked polymer obtained from (meth) acrylic acid hydroxyalkyl ester, methacrylic acid alkylester and a specific crosslinkable monomer is thermoplastic. The present invention was achieved by solving the above problems by laminating a thermoplastic resin composition blended with a resin on the surface of the thermoplastic resin.
【0007】すなわち本発明の要旨は、熱可塑性樹脂
(A)100重量部に対して、アルキル基の炭素数1〜
8の(メタ)アクリル酸ヒドロキシアルキルエステル
(b−1)0.5〜80重量%、アルキル基の炭素数1
〜13のメタクリル酸アルキルエステル(b−2)10
〜99重量%、アルキル基の炭素数1〜8のアクリル酸
アルキルエステル(b−3)0〜79重量%、ビニル芳
香族モノマー(b−4)0〜70重量%およびその他の
モノエチレン性不飽和モノマー(b−5)0〜20重量
%からなる非架橋性モノマー混合物(B−1)95〜1
00重量%未満と分子内に2個以上の二重結合を有する
架橋性モノマー(B−2)0重量%を越えて〜5重量%
とからなる混合物を重合することによって得られる架橋
ポリマー(B)を0.1〜40重量部配合してなる艶消
し性熱可塑性樹脂組成物(I)を少なくとも表面層に有
することを特徴とする熱可塑性樹脂積層物にある。That is, the gist of the present invention is that the carbon number of the alkyl group is 1 to 100 parts by weight of the thermoplastic resin (A).
8 (meth) acrylic acid hydroxyalkyl ester (b-1) 0.5 to 80% by weight, alkyl group having 1 carbon atom
Methacrylic acid alkyl ester (b-2) 10
To 99 wt%, 0 to 79 wt% acrylic acid alkyl ester (b-3) having 1 to 8 carbon atoms of an alkyl group, 0 to 70 wt% vinyl aromatic monomer (b-4), and other monoethylenic Non-crosslinkable monomer mixture (B-1) 95-1 consisting of 0-20% by weight of saturated monomer (b-5)
Less than 00% by weight and more than 0% by weight to 5% by weight of a crosslinkable monomer (B-2) having two or more double bonds in the molecule.
Characterized in that it has a matte thermoplastic resin composition (I) formed by blending 0.1 to 40 parts by weight of a crosslinked polymer (B) obtained by polymerizing a mixture of It is in a thermoplastic resin laminate.
【0008】本発明に用いる熱可塑性樹脂(A)として
はアクリル樹脂、塩化ビニル樹脂、ABS樹脂等を挙げ
ることができ、その中でアクリル樹脂が最も好ましい。
本発明における架橋ポリマー(B)は、非架橋性モノマ
ー混合物(B−1)と架橋性モノマー(B−2)とから
得られるものである。Examples of the thermoplastic resin (A) used in the present invention include acrylic resin, vinyl chloride resin, ABS resin and the like, among which acrylic resin is most preferable.
The crosslinked polymer (B) in the present invention is obtained from the non-crosslinkable monomer mixture (B-1) and the crosslinkable monomer (B-2).
【0009】本発明で使用される非架橋性モノマー混合
物(B−1)は、アルキル基の炭素数1〜8の(メタ)
アクリル酸ヒドロキシアルキルエステル(b−1)0.
5〜80重量%、アルキル基の炭素数1〜13のメタク
リル酸アルキルエステル(b−2)10〜99重量%、
アルキル基の炭素数1〜8のアクリル酸アルキルエステ
ル(b−3)0〜79重量%、ビニル芳香族モノマー
(b−4)0〜70重量%、その他のモノエチレン性不
飽和モノマー(b−5)0〜20重量%から成るもので
ある。The non-crosslinkable monomer mixture (B-1) used in the present invention comprises an alkyl group (meth) having 1 to 8 carbon atoms.
Acrylic acid hydroxyalkyl ester (b-1) 0.
5 to 80% by weight, alkyl group having 1 to 13 carbon atoms of methacrylic acid alkyl ester (b-2) 10 to 99% by weight,
Acrylic acid alkyl ester having 1 to 8 carbon atoms of alkyl group (b-3) 0 to 79% by weight, vinyl aromatic monomer (b-4) 0 to 70% by weight, other monoethylenically unsaturated monomer (b- 5) 0 to 20% by weight.
【0010】アルキル基の炭素数1〜8の(メタ)アク
リル酸ヒドロキシアルキルエステル(b−1)として
は、メタクリル酸2−ヒドロキシエチル、メタクリル酸
2−ヒドロキシプロピル、メタクリル酸2、3−ジヒド
ロキシプロピル、アクリル酸2−ヒドロキシエチル、ア
クリル酸4−ヒドロキシブチル等が挙げることができ、
特にメタクリル酸2−ヒドロキシエチルが好ましい。Examples of the (meth) acrylic acid hydroxyalkyl ester (b-1) having an alkyl group having 1 to 8 carbon atoms include 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate and 2,3-dihydroxypropyl methacrylate. , 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate and the like,
2-Hydroxyethyl methacrylate is particularly preferable.
【0011】アルキル基の炭素数1〜8の(メタ)アク
リル酸ヒドロキシアルキルエステルは非架橋性モノマー
混合物中0.5〜80重量%の範囲で使用することがで
き、さらには1〜40重量%の範囲で使用するのが好ま
しい。0.5重量%未満では艶消し効果が不十分で、一
方80重量%を超えると得られる成形物の表面状態が不
良となる傾向がある。The (meth) acrylic acid hydroxyalkyl ester having 1 to 8 carbon atoms in the alkyl group can be used in the range of 0.5 to 80% by weight in the non-crosslinking monomer mixture, and further 1 to 40% by weight. It is preferable to use in the range of. If it is less than 0.5% by weight, the matting effect is insufficient, while if it exceeds 80% by weight, the surface condition of the obtained molded article tends to be poor.
【0012】メタクリル酸アルキルエステル(b−2)
としては、メタクリル酸メチル、メタクリル酸エチル、
メタクリル酸ブチル等の低級メタクリル酸アルキルエス
テルが挙げられるが、中でもメタクリル酸メチルが好ま
しい。メタクリル酸アルキルエステルは得られる成形物
の表面外観の点から、非架橋性モノマー混合物中10〜
99重量%の範囲で使用される。好ましくは15〜70
重量%の範囲で使用される。Methacrylic acid alkyl ester (b-2)
As, methyl methacrylate, ethyl methacrylate,
Examples thereof include lower methacrylic acid alkyl esters such as butyl methacrylate, with methyl methacrylate being preferred. The methacrylic acid alkyl ester is contained in the non-crosslinkable monomer mixture in an amount of 10 to 10 in terms of the surface appearance of the obtained molded product.
Used in the range of 99% by weight. Preferably 15-70
Used in the weight% range.
【0013】アクリル酸アルキルエステル(b−3)し
ては、アクリル酸エチル、アクリル酸ブチル、アクリル
酸2−エチルヘキシル等の低級アクリル酸アルキルエス
テルが挙げられ、中でもアクリル酸ブチルが好ましい。
アクリル酸アルキルエステルは、非架橋性モノマー混合
物中79重量%までの範囲で使用できる。好ましくは
0.5〜40重量%、さらに好ましくは5〜25重量%
である。Examples of the alkyl acrylate (b-3) include lower acrylic acid alkyl esters such as ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate, with butyl acrylate being preferred.
The alkyl acrylate can be used in the range of up to 79% by weight in the non-crosslinkable monomer mixture. Preferably 0.5-40% by weight, more preferably 5-25% by weight
Is.
【0014】ビニル芳香族モノマー(b−4)として
は、スチレン、ビニルトルエン、α−メチルスチレン、
ハロゲン化スチレン等が挙げられるが、中でもスチレン
が好ましい。ビニル芳香族モノマーは、非架橋性モノマ
ー混合物中70重量%までの範囲で使用できる。好まし
くは10〜60重量%、さらに好ましくは15〜55重
量%である。As the vinyl aromatic monomer (b-4), styrene, vinyltoluene, α-methylstyrene,
Halogenated styrene and the like can be mentioned, but styrene is particularly preferable. The vinyl aromatic monomer can be used in the range of up to 70% by weight in the non-crosslinkable monomer mixture. It is preferably 10 to 60% by weight, more preferably 15 to 55% by weight.
【0015】モノエチレン性不飽和モノマー(b−5)
としては、公知のモノマーが使用可能で例えば、メタク
リル酸、フマール酸、マレイン酸および共重合可能なカ
ルボン酸とそのエステル類のうちアルキル基の炭素数1
〜13メタクリル酸アルキルエステル 、アルキル基の
炭素数1〜8のアクリル酸アルキルエステルを除いたも
の、塩化ビニル、臭化ビニル等のハロゲン化ビニル、酢
酸ビニル等のビニルエステル類、アクリロニトリル等が
挙げられる。モノエチレン性不飽和モノマーは、非架橋
性モノマー混合物中20重量%までの範囲で使用するこ
とができる。好ましくは10重量%である。Monoethylenically unsaturated monomer (b-5)
Known monomers can be used as, for example, methacrylic acid, fumaric acid, maleic acid, and copolymerizable carboxylic acids and their esters, which have 1 carbon atom in the alkyl group.
To 13 methacrylic acid alkyl esters, those excluding alkyl acrylates having 1 to 8 carbon atoms in the alkyl group, vinyl halides such as vinyl chloride and vinyl bromide, vinyl esters such as vinyl acetate, and acrylonitrile. . Monoethylenically unsaturated monomers can be used in the range of up to 20% by weight in the non-crosslinkable monomer mixture. It is preferably 10% by weight.
【0016】架橋性モノマー(B−2)には、分子内に
2個以上の不飽和結合を持つ化合物が用いられる。具体
的にはアリルメタクリレート、トリアリルシアヌレー
ト、トリアリルイソシアヌレート等のアリル基含有架橋
性モノマー、エチレングリコールジメタクリレート等の
アルキレングリコールの不飽和カルボン酸エステル、プ
ロピレングリコールジアリルエーテル等のアルキレング
リコールの不飽和アルコールエーテル、ジビニルベンゼ
ン等の多価ビニルベンゼンなどが挙げられる。As the crosslinkable monomer (B-2), a compound having two or more unsaturated bonds in the molecule is used. Specifically, allyl group-containing crosslinkable monomers such as allyl methacrylate, triallyl cyanurate, and triallyl isocyanurate, unsaturated carboxylic acid esters of alkylene glycol such as ethylene glycol dimethacrylate, and alkylene glycol such as propylene glycol diallyl ether. Examples include saturated alcohol ethers and polyvalent vinylbenzenes such as divinylbenzene.
【0017】特にその2個以上の不飽和結合のうちの少
なくとも1個がアリル基である化合物であることが好ま
しい。上に挙げたアリル基含有架橋性モノマーを用いる
ことにより、架橋ポリマー内部に適度の架橋の組成分布
をもたせることが可能となる。これらの中でも特に、ア
リルメタクリレートが好ましい。架橋性モノマーの添加
量は、非架橋性モノマーと架橋性モノマーの混合物中、
0重量%を越えて〜5重量%である。架橋性モノマーを
添加しない場合、艶消し性が十分でない場合があり、ま
た5重量%を超える場合は、表面状態が悪くなる。Particularly preferred is a compound in which at least one of the two or more unsaturated bonds is an allyl group. By using the above-mentioned allyl group-containing crosslinkable monomer, it becomes possible to provide the crosslinked polymer with a proper crosslink composition distribution. Of these, allyl methacrylate is particularly preferable. The amount of the crosslinkable monomer added is in the mixture of the noncrosslinkable monomer and the crosslinkable monomer,
More than 0% by weight and up to 5% by weight. If the cross-linking monomer is not added, the matting property may not be sufficient, and if it exceeds 5% by weight, the surface condition may be deteriorated.
【0018】本発明の架橋ポリマー(B)は通常の重合
方法によって製造することができるが、特に懸濁重合に
よって得ることが好ましい。The crosslinked polymer (B) of the present invention can be produced by a usual polymerization method, but it is particularly preferably obtained by suspension polymerization.
【0019】懸濁重合の開始剤としては通常の懸濁重合
に使用されるものが用いられ、有機過酸化物、アゾ化合
物を挙げることができる。As the initiator for suspension polymerization, those used in ordinary suspension polymerization are used, and examples thereof include organic peroxides and azo compounds.
【0020】懸濁安定剤としては通常用いられるものが
用いられ、有機コロイド性高分子物質、無機コロイド性
高分子物質、無機微粒子及びこれらと界面活性剤との組
み合わせを挙げることができる。As the suspension stabilizer, those usually used are used, and examples thereof include organic colloidal polymeric substances, inorganic colloidal polymeric substances, inorganic fine particles, and combinations of these with a surfactant.
【0021】メルカプタン等の重合度調節剤を用いるこ
とは可能であり、それらを用いて分子量分布を調節する
方がむしろ好ましい場合が多い。It is possible to use a polymerization degree controlling agent such as mercaptan, and it is often preferable to control the molecular weight distribution using them.
【0022】懸濁重合は通常懸濁安定剤の存在下にモノ
マー類を重合開始剤とともに水性懸濁して行われる。そ
れ以外にもモノマーに可溶な重合物をモノマーに溶かし
込んで使用したり、架橋性モノマーを加えずに一部塊状
で重合した後、架橋性モノマーや懸濁安定剤等を加えて
行うこともできる。The suspension polymerization is usually carried out by suspending the monomers in an aqueous suspension together with a polymerization initiator in the presence of a suspension stabilizer. Other than that, use a polymer that is soluble in the monomer by dissolving it in the monomer, or after partially polymerizing in bulk without adding the crosslinkable monomer, add the crosslinkable monomer or suspension stabilizer, etc. You can also
【0023】架橋ポリマーの生成粒子径は好ましくはは
5〜500μであり、より好ましくは40〜250μで
ある。平均粒子径が5μ未満では、その艶消し性は十分
でなく、逆に500μを超えると得られる成形物の表面
は粗くなり、しかも均一な艶消しが得られにくくなり好
ましくない。The particle size of the crosslinked polymer produced is preferably 5 to 500 μm, more preferably 40 to 250 μm. If the average particle size is less than 5 μ, the matteness is not sufficient, and conversely, if it exceeds 500 μm, the surface of the obtained molded product becomes rough and it is difficult to obtain a uniform matte, which is not preferable.
【0024】架橋ポリマー(B)の配合量は熱可塑性樹
脂(A)100重量部に対して0.1〜40重量部の範
囲であり、艶消し効果の点から1重量部以上を使用する
のが好ましく、さらには3重量部以上を使用するのが好
ましい。The amount of the crosslinked polymer (B) compounded is in the range of 0.1 to 40 parts by weight with respect to 100 parts by weight of the thermoplastic resin (A), and 1 part by weight or more is used from the viewpoint of matting effect. Is preferable, and it is more preferable to use 3 parts by weight or more.
【0025】艶消し性熱可塑性樹脂組成物(I)の混合
方法としては、混合物が同時にせん断圧縮されるような
スクリュー型押出機による混合、加熱ロール間での混
練、バーバリー型ミキサーの如き、加熱高せん断混合装
置中での混合等の適当な方法が一般に用いられる。The matting thermoplastic resin composition (I) can be mixed by a screw type extruder in which the mixture is simultaneously shear-compressed, kneading between heating rolls, heating by a Burberry type mixer, or the like. Appropriate methods such as mixing in a high shear mixer are commonly used.
【0026】艶消し性熱可塑性樹脂組成物(I)は必要
に応じて一般の配合剤、例えば安定剤、滑剤、加工助
剤、耐衝撃助剤、可塑剤、発泡剤、充填剤、着色剤など
を含むことができる。The matte thermoplastic resin composition (I) is a general compounding agent, if necessary, such as a stabilizer, a lubricant, a processing aid, an impact resistance aid, a plasticizer, a foaming agent, a filler and a colorant. Can be included.
【0027】艶消し性熱可塑性樹脂組成物(I)はフィ
ルム状物、シート状物として、アクリル樹脂、ポリカー
ボネート樹脂、塩化ビニル樹脂、ABS樹脂等の熱可塑
性樹脂に積層して本発明の熱可塑性樹脂積層物とする。
特に、アクリル樹脂、ポリカーボネート樹脂が好まし
い。The matte thermoplastic resin composition (I) is laminated in the form of a film or sheet on a thermoplastic resin such as an acrylic resin, a polycarbonate resin, a vinyl chloride resin or an ABS resin to form the thermoplastic resin of the present invention. It is a resin laminate.
In particular, acrylic resin and polycarbonate resin are preferable.
【0028】本発明の熱可塑性樹脂積層物の製造法とし
ては、押出機を用いての共押出成形、押出ラミネーショ
ン成形、熱ラミネーション以外にも、一方のフィルムを
形成した後他の重合体を含む溶液を流延して溶剤を除去
する方法など、特に制限なく公知の積層方法が採用でき
る。The method for producing the thermoplastic resin laminate of the present invention includes, in addition to coextrusion molding using an extruder, extrusion lamination molding and thermal lamination, other polymer after forming one film. A known lamination method can be adopted without particular limitation, such as a method of casting a solution to remove the solvent.
【0029】また、積層物は、表面層と熱可塑性樹脂の
間に中間層を設けることもできる。Further, the laminate may have an intermediate layer between the surface layer and the thermoplastic resin.
【0030】更にこれ積層物は容易に印刷を施すことが
可能でその意匠効果を著しく高めることができる。Further, this laminate can be easily printed and its design effect can be remarkably enhanced.
【0031】[0031]
【実施例】以下、実施例により本発明をさらに詳細に説
明する。なお、下記実施例における部数はすべて重量基
準である。The present invention will be described in more detail with reference to the following examples. In the following examples, all the parts are based on weight.
【0032】また、実施例中で用いた評価方法は下記の
通りである。The evaluation methods used in the examples are as follows.
【0033】(1)60度鏡面光沢度は村上色彩研究所
製、光沢度計GM−26Dを用いて測定した。(1) The 60-degree specular gloss was measured using a gloss meter GM-26D manufactured by Murakami Color Research Laboratory.
【0034】(2)表面状態:分散性の評価の目安とし
て表面状態(粗さ、均一性)を目視評価した。(2) Surface condition: The surface condition (roughness, uniformity) was visually evaluated as a standard for evaluating the dispersibility.
【0035】○:非常に良好 △:普通 ×:不良 実施例1 (1)架橋ポリマー(B)の製造 攪拌機、還流冷却器、窒素ガス導入口等の付いた反応容
器に次の混合物を仕込んだ。◯: Very good Δ: Normal ×: Poor Example 1 (1) Production of crosslinked polymer (B) The following mixture was charged in a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen gas inlet, and the like. .
【0036】 スチレン 30部 アクリル酸ブチル 20部 メタクリル酸メチル 30部 メタクリル酸2−ヒドロキシエチル 20部 アリルメタクリレート 2部 t−ドデシルメルカプタン 0.5部 ラウロイルパーオキサイド 1部 第三リン酸カルシウム 20部 水 250部 容器内を十分に窒素ガスで置換した後、上記混合物の混
合物を攪拌しながら75℃まで加熱し、窒素ガス気流中
で重合を進めた。3時間後に90℃に昇温してさらに4
5分保持して重合を完了し、脱水、乾燥して架橋ポリマ
ービーズを得た。生成ビーズの粒子径は5〜500μ
で、重量平均粒子径は100μ前後であった。得られた
ビーズは次の粒度分布を示した。Styrene 30 parts Butyl acrylate 20 parts Methyl methacrylate 30 parts 2-Hydroxyethyl methacrylate 20 parts Allyl methacrylate 2 parts t-Dodecyl mercaptan 0.5 parts Lauroyl peroxide 1 part Tricalcium phosphate 20 parts Water 250 parts Container After sufficiently replacing the inside with nitrogen gas, the mixture of the above mixture was heated to 75 ° C. with stirring, and the polymerization was advanced in a nitrogen gas stream. After 3 hours, the temperature was raised to 90 ° C and further 4
Polymerization was completed by holding for 5 minutes, dehydrated and dried to obtain crosslinked polymer beads. The particle size of the produced beads is 5-500μ
The weight average particle diameter was around 100 μm. The beads obtained had the following particle size distribution.
【0037】 メッシュ 重量% 32以上 1.0 32〜48 2.4 48〜100 13.3 100〜150 57.1 150〜200 15.1 200〜250 7.6 250〜400 3.2 400以下 0.3 (2)艶消し性熱可塑性樹脂積層物の製造 実施例1(1)で得られた架橋ポリマーをMMAフィル
ム用樹脂(三菱レイヨン(株)製、ハイペットHBS0
01)100部に対して8部配合して混合し、2軸押出
機で、240℃で押し出し切断してペレット化した。得
られたペレットを乾燥後、アクリル樹脂ペレット(三菱
レイヨン(株)製 アクリペットVH)とともに、共押
出成形法で艶消し性熱可塑性樹脂(I)層が100μ、
アクリル樹脂層が2mmとなるように、240℃で成形
し熱可塑性樹脂積層物を得た。その60度鏡面光沢度と
積層物の表面状態を評価した。結果を表1に示す。Mesh weight% 32 or more 1.0 32 to 48 2.4 48 to 100 13.3 100 to 150 57.1 150 to 200 15.1 200 to 250 7.6 250 to 400 3.2 400 or less 0 .3 (2) Manufacture of matte thermoplastic resin laminate The crosslinked polymer obtained in Example 1 (1) was used as a resin for MMA film (manufactured by Mitsubishi Rayon Co., Ltd., Hipet HBS0).
01) 8 parts per 100 parts were mixed and mixed, and extruded and cut at 240 ° C. with a twin-screw extruder to form pellets. After drying the obtained pellets, a matte thermoplastic resin (I) layer of 100 μ was formed by a coextrusion molding method together with an acrylic resin pellet (Acrypet VH manufactured by Mitsubishi Rayon Co., Ltd.).
Molding was performed at 240 ° C. so that the acrylic resin layer had a thickness of 2 mm to obtain a thermoplastic resin laminate. The 60-degree specular gloss and the surface condition of the laminate were evaluated. The results are shown in Table 1.
【0038】[0038]
【表1】 [Table 1]
【0039】実施例2〜8 架橋ポリマー(B)の組成及びMMAフィルム用樹脂へ
の配合量を表1に示す通りに変更した以外は実施例1と
同様に実験を行った。結果を表1に示す。Examples 2 to 8 Experiments were carried out in the same manner as in Example 1 except that the composition of the crosslinked polymer (B) and the amount of the resin for MMA film were changed as shown in Table 1. The results are shown in Table 1.
【0040】実施例9 艶消し性熱可塑性樹脂組成物(I)が積層される熱可塑
性樹脂を、ポリカーボネート樹脂(GEプラスチック製
レキサンML−5500)に変更し、280℃で成形
する以外は実施例1と同様に実験を行った。結果を表1
に示す。Example 9 Example except that the thermoplastic resin on which the matte thermoplastic resin composition (I) was laminated was changed to polycarbonate resin (GE Plastic Lexan ML-5500) and molding was performed at 280 ° C. The experiment was performed in the same manner as 1. The results are shown in Table 1.
Shown in.
【0041】実施例10 艶消し性熱可塑性樹脂組成物が積層される熱可塑性樹脂
を、塩化ビニル樹脂(P=720)100部、安定剤
(ジブチルスズマレエート)3部、耐衝撃助剤(三菱レ
イヨン製、メタブレンC−102)10部、加工助剤
(三菱レイヨン製、メタブレンP−551)1部、滑剤
(ブチルステアレート)1部からなる硬質塩化ビニル樹
脂組成物に変更し、200℃で成形する以外は実施例1
と同様に行った。結果を表1に示す。Example 10 100 parts of a vinyl chloride resin (P = 720), 3 parts of a stabilizer (dibutyl tin maleate), an impact resistance auxiliary agent (Mitsubishi Change to a hard vinyl chloride resin composition consisting of 10 parts of rayon, Metabrene C-102), 1 part of processing aid (Mitsubishi Rayon, metabrene P-551), 1 part of lubricant (butyl stearate), and at 200 ° C. Example 1 except for molding
I went the same way. The results are shown in Table 1.
【0042】実施例11 艶消し性熱可塑性樹脂組成物が積層される熱可塑性樹脂
を、ABS樹脂(三菱レイヨン製 ダイヤペットABS
3001M)に変更し、240℃で成形する以外は実施
例1と同様に行った。結果を表1に示す。Example 11 The thermoplastic resin laminated with the matte thermoplastic resin composition was ABS resin (Diapet ABS manufactured by Mitsubishi Rayon Co., Ltd.).
The same procedure as in Example 1 was performed except that the temperature was changed to 3001M) and the molding was performed at 240 ° C. The results are shown in Table 1.
【0043】実施例12 積層物の製造法を、押出ラミネーション法に変更する以
外は実施例1と同様に実験を行った。具体的にはMMA
フィルム用樹脂(三菱レイヨン(株)製 ハイペットH
BS001)100部に対して、実施例1(1)で得ら
れた架橋ポリマー(B)を8部配合して混合し、2軸押
出機で、240℃で押出し切断してペレット化した。得
られたペレットを乾燥後、T−ダイ法で240℃で製膜
し50μ程度の厚みのフィルムを得た。次に240℃で
アクリル樹脂(三菱レイヨン製アクリペットVH)を押
出成形して2mmシート状に成形する際に、溶融アクリ
ル樹脂と冷却ロールの間に前出フィルムを導入すること
により、押出ラミネーションを行った。結果を表1に示
す。Example 12 An experiment was conducted in the same manner as in Example 1 except that the method for producing the laminate was changed to the extrusion lamination method. Specifically, MMA
Resin for film (HI-PET H manufactured by Mitsubishi Rayon Co., Ltd.)
8 parts of the crosslinked polymer (B) obtained in Example 1 (1) was mixed and mixed with 100 parts of BS001), and the mixture was extruded and cut at 240 ° C. with a twin-screw extruder to be pelletized. After drying the obtained pellets, a film having a thickness of about 50 μm was obtained by T-die method at 240 ° C. Next, when the acrylic resin (Acrypet VH manufactured by Mitsubishi Rayon) is extrusion-molded at 240 ° C. to form a 2 mm sheet, by introducing the above-mentioned film between the molten acrylic resin and the cooling roll, extrusion lamination can be achieved. went. The results are shown in Table 1.
【0044】実施例13 積層物の製造法を、熱ラミネーション法に変更する以外
は実施例1と同様に実験を行った。具体的には実施例1
2で得られたフィルムをエンボス付きラミネートロール
を用い、厚み100μの軟質塩化ビニルフィルムと15
0℃、30kg/cm2の条件で熱ラミネーションを行
った。結果を表1に示す。Example 13 An experiment was conducted in the same manner as in Example 1 except that the method for producing a laminate was changed to the thermal lamination method. Specifically, Example 1
Using the laminating roll with embossing, the film obtained in 2 and 15
Thermal lamination was performed under the conditions of 0 ° C. and 30 kg / cm 2. The results are shown in Table 1.
【0045】比較例1 架橋ポリマー(B)のかわりに架橋性艶消剤(三菱レイ
ヨン メタブレンF410)を8部配合し、実施例1と
同様に実験を行った。結果を表2に示す。Comparative Example 1 Instead of the crosslinked polymer (B), 8 parts of a crosslinkable matting agent (Mitsubishi Rayon Metablen F410) was blended, and the same experiment as in Example 1 was conducted. The results are shown in Table 2.
【0046】比較例2 架橋ポリマー(B)を使用せずに実施例1と同様に成形
し、その60度鏡面光沢度と積層物の表面状態を評価
し、その結果を表1に示した。Comparative Example 2 Molding was carried out in the same manner as in Example 1 without using the crosslinked polymer (B), the 60-degree specular gloss and the surface condition of the laminate were evaluated, and the results are shown in Table 1.
【0047】比較例3 架橋ポリマー(B)の組成を表1に示す通りにした以外
は実施例1と同様に実験を行った。結果を表1に示す。Comparative Example 3 An experiment was conducted in the same manner as in Example 1 except that the composition of the crosslinked polymer (B) was changed as shown in Table 1. The results are shown in Table 1.
【0048】[0048]
【発明の効果】本発明の熱可塑性樹脂積層物は、表面状
態を損なわずに、従来の艶消剤を用いた場合には不十分
であった艶消性が大きく改善されるので、工業上優れた
効果を奏する。INDUSTRIAL APPLICABILITY The thermoplastic resin laminate of the present invention greatly improves the mattness which was insufficient when the conventional matting agent was used, without impairing the surface condition, and thus is industrially useful. It has an excellent effect.
Claims (1)
成物(I)を少なくとも表面層に有することを特徴とす
る熱可塑性樹脂積層物。 艶消し性熱可塑性樹脂組成物(I) 熱可塑性樹脂(A)100重量部に対して、アルキル基
の炭素数1〜8の(メタ)アクリル酸ヒドロキシアルキ
ルエステル(b−1)0.5〜80重量%、アルキル基
の炭素数1〜13のメタクリル酸アルキルエステル(b
−2)10〜99重量%、アルキル基の炭素数1〜8の
アクリル酸アルキルエステル(b−3)0〜79重量
%、ビニル芳香族モノマー(b−4)0〜70重量%お
よびその他のモノエチレン性不飽和モノマー(b−5)
0〜20重量%からなる非架橋性モノマー混合物(B−
1)95〜100重量%未満と分子内に2個以上の二重
結合を有する架橋性モノマー(B−2)0重量%を越え
て〜5重量%とからなる混合物を重合することによって
得られる架橋ポリマー(B)を0.1〜40重量部配合
してなる艶消し性熱可塑性樹脂組成物。1. A thermoplastic resin laminate comprising a matte thermoplastic resin composition (I) shown below in at least a surface layer. Matting thermoplastic resin composition (I) 0.5- (meth) acrylic acid hydroxyalkyl ester (b-1) having 1 to 8 carbon atoms of an alkyl group based on 100 parts by weight of the thermoplastic resin (A). 80% by weight, alkyl methacrylate having 1 to 13 carbon atoms (b)
-2) 10 to 99% by weight, 0 to 79% by weight of an alkyl acrylate having 1 to 8 carbon atoms of an alkyl group (b-3), 0 to 70% by weight of a vinyl aromatic monomer (b-4) and other Monoethylenically unsaturated monomer (b-5)
Non-crosslinkable monomer mixture (B-
1) Obtained by polymerizing a mixture consisting of 95 to less than 100% by weight and more than 0 to 5% by weight of a crosslinkable monomer (B-2) having two or more double bonds in the molecule. A matte thermoplastic resin composition comprising 0.1 to 40 parts by weight of a crosslinked polymer (B).
Priority Applications (1)
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JP6110019A JP3035444B2 (en) | 1994-05-24 | 1994-05-24 | Thermoplastic resin laminate |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP6110019A JP3035444B2 (en) | 1994-05-24 | 1994-05-24 | Thermoplastic resin laminate |
Publications (2)
Publication Number | Publication Date |
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JPH07314615A true JPH07314615A (en) | 1995-12-05 |
JP3035444B2 JP3035444B2 (en) | 2000-04-24 |
Family
ID=14525069
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JP6110019A Expired - Lifetime JP3035444B2 (en) | 1994-05-24 | 1994-05-24 | Thermoplastic resin laminate |
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JP (1) | JP3035444B2 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000212293A (en) * | 1999-01-21 | 2000-08-02 | Elf Atochem Sa | Polymer article having textured surface and matte appearance |
WO2000064983A1 (en) * | 1999-04-23 | 2000-11-02 | Kaneka Corporation | Processing aid for thermoplastic resin and thermoplastic resin composition containing the same |
WO2009025334A1 (en) | 2007-08-21 | 2009-02-26 | Umg Abs, Ltd. | Method for producing enlarged rubber, graft copolymer, thermoplastic resin composition and molded article |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR102712234B1 (en) | 2024-04-08 | 2024-09-30 | 김윤모 | Dental carving utility handpiece safehold apparatus |
-
1994
- 1994-05-24 JP JP6110019A patent/JP3035444B2/en not_active Expired - Lifetime
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000212293A (en) * | 1999-01-21 | 2000-08-02 | Elf Atochem Sa | Polymer article having textured surface and matte appearance |
WO2000064983A1 (en) * | 1999-04-23 | 2000-11-02 | Kaneka Corporation | Processing aid for thermoplastic resin and thermoplastic resin composition containing the same |
US7105602B1 (en) | 1999-04-23 | 2006-09-12 | Kaneka Corporation | Processing aid for thermoplastic resin and thermoplastic resin composition containing the same |
WO2009025334A1 (en) | 2007-08-21 | 2009-02-26 | Umg Abs, Ltd. | Method for producing enlarged rubber, graft copolymer, thermoplastic resin composition and molded article |
Also Published As
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JP3035444B2 (en) | 2000-04-24 |
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