JPH05220859A - Surface-cured thermoplastic resin molding and method for producing the same - Google Patents
Surface-cured thermoplastic resin molding and method for producing the sameInfo
- Publication number
- JPH05220859A JPH05220859A JP4867491A JP4867491A JPH05220859A JP H05220859 A JPH05220859 A JP H05220859A JP 4867491 A JP4867491 A JP 4867491A JP 4867491 A JP4867491 A JP 4867491A JP H05220859 A JPH05220859 A JP H05220859A
- Authority
- JP
- Japan
- Prior art keywords
- thermoplastic resin
- resin molded
- cured
- molded product
- curing
- 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.)
- Withdrawn
Links
- 229920005992 thermoplastic resin Polymers 0.000 title claims abstract description 53
- 238000000465 moulding Methods 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 239000013043 chemical agent Substances 0.000 claims abstract description 5
- 239000000178 monomer Substances 0.000 claims description 24
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims description 13
- 239000004925 Acrylic resin Substances 0.000 claims description 12
- 239000004417 polycarbonate Substances 0.000 claims description 11
- 229920000515 polycarbonate Polymers 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 7
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 6
- 238000011417 postcuring Methods 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 24
- 238000000576 coating method Methods 0.000 description 14
- 238000001723 curing Methods 0.000 description 13
- 239000011248 coating agent Substances 0.000 description 12
- 239000010410 layer Substances 0.000 description 12
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 239000003814 drug Substances 0.000 description 5
- 229940079593 drug Drugs 0.000 description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 239000002344 surface layer Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000004431 polycarbonate resin Substances 0.000 description 3
- 229920005668 polycarbonate resin Polymers 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- GKZPEYIPJQHPNC-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)CO GKZPEYIPJQHPNC-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000000088 plastic resin Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 238000007666 vacuum forming Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Landscapes
- Macromonomer-Based Addition Polymer (AREA)
- Polymerisation Methods In General (AREA)
Abstract
(57)【要約】
【目的】表面の耐擦傷性、硬度、耐候性を向上させ、更
に表面保護膜と基材との密着性に優れた非平面を持つ熱
可塑性樹脂成形品及びその製造法にある。
【構成】表面を硬化させた非平面を有する熱可塑性樹脂
成形物において、板状熱可塑性樹脂成形物に、表面を硬
化させる薬剤を塗布した後、粘着性がなく、完全硬化に
至らない状態まで、前硬化させた後、非平面を有する熱
可塑性樹脂成形物に成形し、しかる後、後硬化させるこ
と。
【効果】成形が極めて容易となり、しかも、表面は高強
度で耐擦傷性に極めて優れ、かつ耐候性に優れると共
に、母材とする熱可塑性樹脂層と表面との密着性及び透
明性に極めて優れている。(57) [Abstract] [Purpose] A thermoplastic resin molded article having a non-planar surface which has improved scratch resistance, hardness and weather resistance of the surface and has excellent adhesion between the surface protective film and the substrate, and a method for producing the same. It is in. [Structure] In a thermoplastic resin molded product having a non-planar surface that has been hardened, after applying a chemical agent that hardens the surface to the plate-shaped thermoplastic resin molded product, there is no tackiness and it does not reach full cure After pre-curing, it is molded into a thermoplastic resin molded product having a non-planar surface, and then post-cured. [Effect] Molding is extremely easy, and the surface has high strength, excellent scratch resistance, and weather resistance, and the adhesion and transparency between the thermoplastic resin layer as the base material and the surface are also excellent. ing.
Description
【０００１】〔産業上の利用分野〕本発明は、表面を硬
化させた非平面を有する熱可塑性樹脂成形物及びその製
造法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin molded product having a non-flat surface whose surface is hardened and a method for producing the same.
【０００２】[0002]
【従来の技術】従来、表層と内層とを異種の熱可塑性樹
脂により、剛性、表面硬さ、耐熱性、並びに、耐衝撃性
を改善するための積層成形品などが知られている。例え
ば、特公平１−２２１５１公報の如き、 表層を２軸配
向したポリメチルメタクリル−ト、内層をポリカ−ボネ
−トとを一体接着した積層成形品で、現在、例えば、合
成樹脂製の車両グレ−ジング材として、ポリメチルメタ
クリル−ト及びポリカ−ボネ−トのシ−トが一般に使用
されている。しかし、ポリメチルメタクリル−トは剛
性、表面硬さ、耐候性に優れているか、耐衝撃性と耐熱
性が低い。ポリカ−ボネ−トは耐衝撃性と耐熱性に優れ
ているが、剛性、表面硬さが低い。これら両者の特性を
生かして、表層を２軸配向したポリメチルメタクリル−
トにすることにより、剛性、表面硬さ、耐候性を出し、
内層をポリカ−ボネ−トにすることにより耐衝撃性と耐
熱性を出していることは前述公報からも知られていると
ころである。しかしながら、この製品を実際に製造する
場合は、表層と内層を押出成形ないしは、圧延成形によ
って製造されているのが実状である。従って、強固な積
層成形品は形成されるが、平面積層成形品であって、加
工部品などに使用される非平面状の積層体は加工が困難
であり、又、強く加工することによって、表面剥離ない
し、割れの発生する問題がある。2. Description of the Related Art Conventionally, there have been known laminated molded articles for improving rigidity, surface hardness, heat resistance, and impact resistance by using different thermoplastic resins for the surface layer and the inner layer. For example, as in Japanese Patent Publication No. 22151/1991, it is a laminated molded article in which a surface layer is biaxially oriented polymethylmethacrylate and an inner layer is integrally bonded with polycarbonate. Sheets of polymethylmethacrylate and polycarbonate are generally used as the glazing material. However, polymethyl methacrylate is excellent in rigidity, surface hardness and weather resistance, or is low in impact resistance and heat resistance. Polycarbonate is excellent in impact resistance and heat resistance, but low in rigidity and surface hardness. Taking advantage of the characteristics of both of these, polymethyl methacryl-containing biaxially oriented surface layer
Rigidity, surface hardness, and weather resistance,
It is known from the above-mentioned publication that impact resistance and heat resistance are obtained by using polycarbonate for the inner layer. However, when this product is actually manufactured, it is the actual situation that the surface layer and the inner layer are manufactured by extrusion molding or rolling molding. Therefore, although a strong laminated molded product is formed, it is a planar laminated molded product, and it is difficult to process a non-planar laminated body used for processed parts, etc. There is a problem of peeling or cracking.
【０００３】また、一方、ポリカ−ボネ−ト成形品の表
面特性を改善するために、成形品の表面に塗料を塗布す
る、試みも従来から種々提案されている。 例えば、熱
硬化性のメラミン樹脂塗料を塗布して熱硬化によって保
護皮膜を形成する方法等がある。しかしながら、これら
の加熱硬化によって保護膜を形成する方法では、ある一
定の形状を有する成形品を製造する場合には、あらかじ
め一定の形状に成形したものの表面に塗布して熱硬化す
る製造方法に限定せざるを得ない。また硬化保護皮膜を
平面状の熱可塑性樹脂に形成させた後熱成形を行うと、
硬化保護皮膜に割れが生じたり剥離を生じたりするなど
の問題が生じ実用に供し得る物ではなかった。On the other hand, various attempts have heretofore been proposed to apply a coating material to the surface of a molded article in order to improve the surface characteristics of the molded article. For example, there is a method of applying a thermosetting melamine resin coating and forming a protective film by thermosetting. However, these methods of forming a protective film by heat curing are limited to a manufacturing method in which a molded product having a certain fixed shape is applied in advance to the surface of a molded product having a certain fixed shape and then heat-cured. I have to do it. When a thermosetting resin is applied after forming a hardening protective film on a planar thermoplastic resin,
The cured protective film had problems such as cracking and peeling, and was not suitable for practical use.
【０００４】[0004]
【発明が解決しようとする課題】本発明の目的は非平面
成形品に表面を硬化させる薬剤を塗布後硬化させること
による操作の煩雑さをのぞき塗布を連続的に行うことに
より全工程を大幅に単純化して得られる成形品及びその
製造法を提供しようとするものであり、他の一つの目的
は半硬化の状態で成形出来ることにより通常のシ−ト状
物と同様の取扱い性を有しながら非平面をもつ熱可塑性
樹脂成形品及びその製造法を提供しようとするものであ
り、他の一つの目的は前述、従来技術の欠点を解決し、
ある加工製品を、塗布工程、前硬化工程、加工成形工
程、後硬化工程の連続適工程によって製造を可能にした
表面の耐擦傷性、硬度、耐候性を向上させ、更に表面保
護膜と基材との密着性に優れた非平面を持つ熱可塑性樹
脂成形品及びその製造法を提供しようとするものであ
る。DISCLOSURE OF THE INVENTION The object of the present invention is to perform all the steps by continuously performing the coating except for the complexity of the operation of coating and curing the non-planar molded article with the agent for curing the surface. Another object of the present invention is to provide a molded product obtained by simplification and a manufacturing method thereof. Another purpose is to be able to mold in a semi-cured state so that it has handleability similar to a normal sheet-like product. While providing a thermoplastic resin molded product having a non-planar surface and a method for producing the same, another one of the objects is to solve the above-mentioned drawbacks of the prior art,
Improves scratch resistance, hardness, and weather resistance of the surface by making it possible to manufacture a certain processed product by a continuous suitable process such as coating process, pre-curing process, processing molding process, and post-curing process. It is intended to provide a thermoplastic resin molded product having a non-planar surface excellent in adhesion with and a method for producing the same.
【０００５】[0005]
【課題を解決するための手段】上述した問題点を解決
し、その目的を達成するための本発明の構成は次の通り
である。 （１）表面を硬化させた非平面を有する熱可塑性樹脂成
形物において、板状熱可塑性樹脂成形物に、表面を硬化
させる薬剤を塗布した後、粘着性がなく、完全硬化に至
らない状態まで、前硬化させた後、非平面を有する熱可
塑性樹脂成形物に成形し、しかる後、後硬化させること
を特徴とする表面を硬化させた熱可塑性樹脂成形物。 （２）表面を硬化させる薬剤が、エポキシアクリレ−ト
樹脂モノマ−を含有する請求項第１項記載の表面を硬化
させた熱可塑性樹脂成形物。 （３）表面を硬化させる薬剤が、エポキシアクリレ−ト
樹脂モノマ−とその他の多官能（メタ）アクリレ−ト、
必要により単官能モノマ−、溶剤からなり、反応性モノ
マ−全体中のエポキシアクリレ−ト樹脂モノマ−の割合
が１０〜６０重量％である請求項第１項記載の表面を硬
化させた熱可塑性樹脂成形物。 （４）熱可塑性樹脂がポリカ−ボネ−ト及びポリメチル
メタアクリレ−トである請求項第１項記載の表面を硬化
させた熱可塑性樹脂成形物。 （５） 表面を硬化させた非平面を有する熱可塑性樹脂
成形物の製造方法において、板状熱可塑性樹脂成形物
に、表面を硬化させる薬剤を塗布する工程、粘着性がな
く、完全硬化に至らない状態まで、前硬化させる工程、
引き続き、非平面を有する熱可塑性樹脂成形物に成形す
る工程、該成形する工程後に、後硬化させる工程を順次
行うことを特徴とする表面を硬化させた非平面を有する
熱可塑性樹脂成形物の製造法にある。The structure of the present invention for solving the above-mentioned problems and achieving the object is as follows. (1) In a thermoplastic resin molded product having a non-planar surface that has been hardened, after applying a chemical agent that hardens the surface to the plate-shaped thermoplastic resin molded product, there is no tackiness and it does not reach a state where it is not completely cured. A surface-cured thermoplastic resin molded article characterized by being pre-cured and then molded into a thermoplastic resin molded article having a non-planar surface, and then post-cured. (2) The surface-cured thermoplastic resin molded article according to claim 1, wherein the surface-curing agent contains an epoxy acrylate resin monomer. (3) The agent for curing the surface is an epoxy acrylate resin monomer and other polyfunctional (meth) acrylate,
The surface-cured thermoplastic resin according to claim 1, wherein a monofunctional monomer and a solvent are contained if necessary, and the proportion of the epoxy acrylate resin monomer in the whole reactive monomer is 10 to 60% by weight. Resin molding. (4) The surface-cured thermoplastic resin molding according to claim 1, wherein the thermoplastic resin is polycarbonate or polymethylmethacrylate. (5) In the method for producing a thermoplastic resin molded product having a non-planar surface of which the surface is cured, a step of applying a chemical agent for curing the surface to the plate-shaped thermoplastic resin molded product, which has no tackiness and is completely cured. Pre-curing process until there is no state,
Successively, a step of molding into a thermoplastic resin molded product having a non-planar surface, and a step of post-curing after the molding step are sequentially carried out, and production of a thermoplastic resin molded product having a non-planar surface-hardened surface. In law.
【０００６】以下本発明について詳細に説明する。本発
明における熱可塑性樹脂としては、ポリスチレン、ＡＢ
Ｓ、ＡＳ、ＭＳをはじめ多くのビニル化合物の付加重合
体、ポリカ−ボネ−ト（ＰＣ）及びＰＣを５０％以上含
むアロイ、ポリメチルメタクリ−ト（ＰＭＭＡ）が望ま
しい。The present invention will be described in detail below. Examples of the thermoplastic resin in the present invention include polystyrene and AB
Addition polymers of many vinyl compounds such as S, AS and MS, polycarbonate (PC) and alloys containing 50% or more of PC and polymethylmethacrylate (PMMA) are preferable.
【０００７】次に板状可塑性樹脂に塗布して表面を硬化
させる薬剤としては、エポキシアクリレ−ト樹脂モノマ
−とその他の多官能（メタ）アクリレ−ト、必要により
単官能モノマ−、溶剤からなり、反応性モノマ−全体中
のエポキシアクリレ−ト樹脂モノマ−の割合が１０〜６
０重量％であることが望ましい。この場合、本発明にい
うエポキシアクリレ−ト樹脂モノマ−とは、下記式Ιの
構造を有するもの（ただし、ＲはＨ又は低級アルキル基
を示し、Ｒ´はＨ又はＣＨを示す。ｎ＝０〜２０の整数
である。）Next, as a chemical agent which is applied to the plate-shaped plastic resin to cure the surface, epoxy acrylate resin monomer and other polyfunctional (meth) acrylate, if necessary, monofunctional monomer and solvent are used. The ratio of the epoxy acrylate resin monomer in the whole reactive monomer is 10-6.
It is preferably 0% by weight. In this case, the epoxy acrylate resin monomer referred to in the present invention has a structure of the following formula I (wherein R represents H or a lower alkyl group, and R'represents H or CH. N = It is an integer of 0 to 20.)
【化１】 を言う。なお、上記式Ι中のｎを限定した理由は、ｎが
大きすぎると溶液の粘度が極端に高くなり、塗布の作業
性が悪くなり、平滑な膜が得がたいことから、エポキシ
アクリレ−ト樹脂モノマ−の分子量は、ｎ＝２０以下、
好ましくは、ｎ＝１５以下が良い。又同様に、〔Ｉ〕式
のエポキシアクリレ−ト樹脂モノマ−が反応性モノマ−
全体中の６０重量％を超えると粘度が極端に高くなり、
塗布の作業性が悪く、１０重量％未満では平滑な膜が得
がたくなる。このことから、〔１〕式のエポキシアクリ
レ−ト樹脂モノマ−は反応性モノマ−全体中の１０〜６
０重量％、好ましくは１５〜５０重量％が良い。[Chemical 1] Say The reason for limiting n in the above formula Ι is that when n is too large, the viscosity of the solution becomes extremely high, the workability of coating becomes poor, and it is difficult to obtain a smooth film. The molecular weight of the monomer is n = 20 or less,
It is preferable that n = 15 or less. Similarly, the epoxy acrylate resin monomer of the formula [I] is a reactive monomer.
If it exceeds 60% by weight of the whole, the viscosity becomes extremely high,
The workability of coating is poor, and if it is less than 10% by weight, it becomes difficult to obtain a smooth film. From this fact, the epoxy acrylate resin monomer of the formula [1] is 10 to 6 in the whole reactive monomer.
0% by weight, preferably 15 to 50% by weight is good.
【０００８】また、 その他の多官能（メタ）アクリレ
−トとしては、トリメチロ−ルプロパントリ（メタ）ア
クリレ−ト、トリメチロ−ルエタントリ（メタ）アクリ
レ−ト、ペンタエリスリト−ルテトラ（メタ）アクリレ
−ト、ペンタエリスリト−ルヘキサアクリレ−ト等の３
価以上の脂肪族多価アルコ−ルのポリ（メタ）アクリレ
−ト類、またノボラックエポキシアクリレ−トなどを掲
げることができる。さらに、前記の単官能モノマ−とし
ては、メタクリル酸メチル、メタクリル酸エチル、メタ
クリル酸シクロヘキシル、メタクリル酸、アクリル酸、
アクリル酸メチル等の（メタ）アクリル酸およびそのエ
ステル等があげられる。次に、塗布して表面を硬化させ
る薬剤中の反応性モノマ−全体の割合は、１０〜９７重
量％の範囲にあることが望ましい。９７％を超えると熱
可塑性樹脂、例えば、ポリカ−ボネ−トとの密着性に劣
り、１０％未満であると、均一なコ−テイングが困難に
なる。また、用途により硬化を小さくしてもよい場合
は、塗布粘度を調整する場合に単官能性モノマ−を用い
るのも有効な方法である。Other polyfunctional (meth) acrylates include trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 3 such as pentaerythritol hexaacrylate
Examples thereof include poly (meth) acrylates of aliphatic polyvalent alcohol having a valence of 3 or more, and novolac epoxy acrylate. Further, as the monofunctional monomer, methyl methacrylate, ethyl methacrylate, cyclohexyl methacrylate, methacrylic acid, acrylic acid,
Examples thereof include (meth) acrylic acid such as methyl acrylate and esters thereof. Next, it is desirable that the ratio of the entire reactive monomer in the drug which is applied to cure the surface is in the range of 10 to 97% by weight. If it exceeds 97%, the adhesion to a thermoplastic resin such as polycarbonate will be poor, and if it is less than 10%, uniform coating becomes difficult. Further, when the curing may be reduced depending on the use, it is an effective method to use a monofunctional monomer when adjusting the coating viscosity.
【０００９】また、本発明で使用する溶剤としては、熱
可塑性樹脂、例えば、ポリカ−ボネ−トの良容媒である
メチルエチルケトン、酢酸エチル、エチルセロソルブア
セテ−ト等が適当で、これらは前述の固形分を除いたも
ので３〜９０重量％の範囲とすることがよい。従って、
膜を形成させるべく溶液の濃度は、前記範囲から適宜選
定されれば良い。The solvent used in the present invention is preferably a thermoplastic resin such as methyl ethyl ketone, ethyl acetate, ethyl cellosolve acetate, which is a good solvent for polycarbonate, and these are mentioned above. It is preferable that the solid content is excluded from the range of 3 to 90% by weight. Therefore,
The concentration of the solution for forming the film may be appropriately selected from the above range.
【００１０】次に製造法について、図面に従って説明す
る。図１（ａ）（ｂ）は本発明に係る熱可塑性樹脂組成
物の製造工程図を示す。図１（ａ）は板状熱可塑性樹脂
成形物の表面に薬剤を塗布した状態を示すもので、１は
板状熱可塑性樹脂で、該板状熱可塑性層の表面に薬剤を
塗布するものである。その薬剤としては、例えば、前述
エポキシアクリレ−ト樹脂モノマ−を主成分とした混合
組成物を用いて、板状熱可塑性樹脂層上に塗布する。２
はこの塗布層をいう。また、この場合、混合物の塗布は
スプレ−、浸漬、ロ−ルコ−テイング等と言ったよう
な、良く知られた方法で、これらいずれかを用いて板状
熱可塑性樹脂層上に塗布しても良い。通常この混合組成
物は、乾燥膜厚として、約１０〜１００μｍの乾燥保護
コ−テイングを得るのに充分な量で塗布する。この場
合、最適の溶媒系は選択した塗布法に応じて変わり得
る。例えば、スプレ−塗布や浸漬法には低粘度の溶媒系
を用い、ロ−ルコ−テングの場合には粘度が高めの溶媒
系を用いる。このように膜厚を調整して塗布した後、必
要に応じて乾燥し、硬化剤の表面をＵＶ水銀灯を用いて
光硬化させる。このときの硬化状態は成形加工するに当
って障害とならない程度、すなわち、成形加工する際、
粘着性があると成形機の金型に付着し、成形シ−トが破
損したり、表面に傷付き、目的とする成形品が得られな
い。従って粘着性がない状態が必要である。また完全硬
化させると成形加工するに当たっては、強固な積層成形
が形成されるが、加工部品を加工することが困難とな
る。 従って、完全硬化に至らない状態の前硬化処理を
する必要がある。そのような状態の板状熱可塑性樹脂層
を図１（ｂ）の如く、成形加工する。成形加工方法とし
ては真空成形、プレス成形、プラグリング成形、圧空成
形等あるが、成形法には、特に、限定されるものではな
いが、特にプレス成形が望ましい。そして成形した非平
面状の熱可塑性樹脂層３を形成した後、引き続き、ＵＶ
硬化によって、後硬化させ熱可塑性樹脂成形物を製造す
る。Next, the manufacturing method will be described with reference to the drawings. 1 (a) and 1 (b) show manufacturing process diagrams of the thermoplastic resin composition according to the present invention. FIG. 1 (a) shows a state in which a drug is applied to the surface of a plate-shaped thermoplastic resin molded article, 1 is a plate-shaped thermoplastic resin, and the drug is applied to the surface of the plate-shaped thermoplastic layer. is there. As the drug, for example, a mixed composition containing the above-mentioned epoxy acrylate resin monomer as a main component is used and applied onto the plate-like thermoplastic resin layer. Two
Means this coating layer. Further, in this case, the mixture is applied onto the plate-like thermoplastic resin layer by any one of well-known methods such as spraying, dipping, roll coating and the like. Is also good. Usually, the mixed composition is applied in an amount sufficient to obtain a dry protective coating having a dry film thickness of about 10 to 100 μm. In this case, the optimum solvent system may vary depending on the coating method chosen. For example, a low viscosity solvent system is used for spray coating and dipping, and a high viscosity solvent system is used for roll coating. After the film thickness is adjusted and applied in this way, it is dried if necessary, and the surface of the curing agent is photocured using a UV mercury lamp. The cured state at this time is such that it does not hinder the molding process, that is, during the molding process,
If it is tacky, it adheres to the mold of the molding machine, the molding sheet is damaged, and the surface is scratched, and the desired molded product cannot be obtained. Therefore, a state without tackiness is required. Further, when it is completely cured, a strong laminated molding is formed in the molding process, but it becomes difficult to process the processed part. Therefore, it is necessary to carry out a pre-curing treatment in a state where complete curing is not achieved. The plate-like thermoplastic resin layer in such a state is molded as shown in FIG. The forming method includes vacuum forming, press forming, plug ring forming, pressure forming and the like. The forming method is not particularly limited, but press forming is particularly desirable. After forming the molded non-planar thermoplastic resin layer 3, UV is continuously applied.
By curing, it is post-cured to produce a thermoplastic resin molded product.
【００１１】[0011]
【実施例】 表面に塗布する薬剤として、 式（Ι）においてｎ＝１、Ｒ＝Ｈの化合物 ６０重量部 ジペンタエリスリト−ルヘキサアクリレ−ト ４０重量部 溶媒（メチルエチルケトン） １００重量部 増感剤（１−ヒドロキシシクロヘキシ−ルフェニ−ルケトン） ５重量部 を調合し、コ−タ−を用いて２ｍｍ厚さのポリカ−ボネ
−ト樹脂板に乾燥厚み２０μｍになるように塗布した。
乾燥後、４００ｗ−ＵＶ水銀灯を３秒間照射し前硬化さ
せた。本シ−トを１７０℃に加熱後、お椀状にプレス成
形した。再度、同種の水銀灯にて１０秒間照射し、後硬
化させた。この結果、得られたお椀状のポリカ−ボネ−
ト樹脂成形体は透明でポリカ−ボネ−ト樹脂と表面硬化
物との密着性は、碁盤目テスト・ＪＩＳＫ−５４００に
て１００／１００であり、かつ擦傷性はスチ−ルウ−ル
で擦っても全く疵が付かなかった。これに対して、同様
にして、表面に塗布する薬剤を塗布乾燥後同種の水銀灯
にて１２秒間照射して硬化させたポリカ−ボネ−ト樹脂
板をプレス成形した物は硬化塗膜にひび割れが発生し
た。Examples As a drug to be applied to the surface, a compound of formula (I) in which n = 1 and R = H 60 parts by weight Dipentaerythritol hexahexaacrylate 40 parts by weight Solvent (methyl ethyl ketone) 100 parts by weight Sensitizer ( 1-Hydroxycyclohexyl phenyl ketone) 5 parts by weight was prepared and coated on a polycarbonate resin plate having a thickness of 2 mm to a dry thickness of 20 μm using a coater.
After drying, it was pre-cured by irradiating with a 400w-UV mercury lamp for 3 seconds. After heating this sheet to 170 ° C., it was press-formed into a bowl shape. Again, it was irradiated with the same kind of mercury lamp for 10 seconds to be post-cured. As a result, the obtained bowl-shaped polycarbonate
The resin molded product is transparent, the adhesion between the polycarbonate resin and the surface-cured product is 100/100 according to the cross-cut test JISK-5400, and the scratch resistance is obtained by rubbing with a steel wheel. There was no flaw at all. On the other hand, in the same manner, a product obtained by press-molding a polycarbonate resin plate which was cured by irradiating with a mercury lamp of the same kind for 12 seconds after coating and drying the chemical to be applied to the surface, had a crack in the cured coating film. Occurred.
【００１２】[0012]
【発明の効果】以上述べたように、二段ＵＶ照射による
硬化によって、成形が極めて容易となり、従って各種形
状の成形を可能とし、しかも成形された熱可塑性樹脂成
形品の表面は高強度で耐擦傷性に極めて優れ、かつ耐候
性に優れると共に、母材とする熱可塑性樹脂層と表面と
の密着性も極めて優れている。従ってプラスチックス本
来のもつ軽量、透明等の性質を保持した状態で、なお表
面特性に優れた成形品を安価に製造出来るので、自動車
用部品等に、実用上極めて有利なものである。As described above, the curing by the two-stage UV irradiation makes the molding extremely easy, and thus enables the molding of various shapes, and the surface of the molded thermoplastic resin molded article has high strength and resistance. It has excellent scratch resistance and weather resistance, and also has excellent adhesion between the thermoplastic resin layer as the base material and the surface. Therefore, molded products having excellent surface characteristics can be manufactured at low cost while maintaining the properties such as lightness and transparency inherent in plastics, which is extremely advantageous in practical use for automobile parts and the like.
【００１３】[0013]
【図１】（ａ）は本発明に係る熱可塑性樹脂組成物の製
造工程断面図を示す。（ｂ）は成形加工後の非平面状の
熱可塑性樹脂層を示す図である。FIG. 1 (a) is a sectional view showing a step of producing a thermoplastic resin composition according to the present invention. (B) is a figure which shows the non-planar thermoplastic resin layer after shaping | molding process.
１ 板状熱可塑性樹脂 ２ 塗布層 ３ 非平面状の熱可塑性樹脂層。 1 plate-like thermoplastic resin 2 coating layer 3 non-planar thermoplastic resin layer.
【手続補正書】[Procedure amendment]
【提出日】平成５年１月５日[Submission date] January 5, 1993
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】請求項５[Name of item to be corrected] Claim 5
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【手続補正２】[Procedure Amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】発明の詳細な説明[Name of item to be amended] Detailed explanation of the invention
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【発明の詳細な説明】Detailed Description of the Invention
【手続補正３】[Procedure 3]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００１[Correction target item name] 0001
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【０００１】 [0001]
【産業上の利用分野】 本発明は、表面を硬化させた非平
面を有する熱可塑性樹脂成形物及びその製造法に関する
ものである。 BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin molded product having a non-flat surface whose surface is hardened, and a method for producing the same.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 寺本 武郎 神奈川県川崎市中原区井田1618番地 新日 本製鐵株式会社第１技術研究所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Takeo Teramoto 1618 Ida, Nakahara-ku, Kawasaki-shi, Kanagawa Shin-Nippon Steel Co., Ltd.
Claims (5)
性樹脂成形物において、板状熱可塑性樹脂成形物に、表
面を硬化させる薬剤を塗布した後、粘着性がなく、完全
硬化に至らない状態まで、前硬化させた後、非平面を有
する熱可塑性樹脂成形物に成形し、しかる後、後硬化さ
せることを特徴とする表面を硬化させた熱可塑性樹脂成
形物。1. A thermoplastic resin molded product having a non-planar surface, the surface of which is not tacky and does not completely cure after the plate-shaped thermoplastic resin molded product is coated with an agent for curing the surface. A surface-cured thermoplastic resin molded article characterized by being pre-cured to a state and then molded into a thermoplastic resin molded article having a non-planar surface, and then post-cured.
リレ−ト樹脂モノマ−を含有する請求項第１項記載の表
面を硬化させた熱可塑性樹脂成形物。2. The surface-cured thermoplastic resin molded article according to claim 1, wherein the surface-curing agent contains an epoxy acrylate resin monomer.
リレ−ト樹脂モノマ−とその他の多官能（メタ）アクリ
レ−ト、必要により単官能モノマ−、溶剤からなり、
反応性モノマ−全体中のエポキシアクリレ−ト樹脂モノ
マ−の割合が１０〜６０重量％である請求項第１項記載
の表面を硬化させた熱可塑性樹脂成形物。3. The surface-curing agent comprises an epoxy acrylate resin monomer and other polyfunctional (meth) acrylate, optionally a monofunctional monomer, and a solvent,
The surface-cured thermoplastic resin molded article according to claim 1, wherein the proportion of the epoxy acrylate resin monomer in the whole reactive monomer is 10 to 60% by weight.
リメチルメタアクリレ−トである請求項第１項記載の表
面を硬化させた熱可塑性樹脂成形物。4. The surface-cured thermoplastic resin molded product according to claim 1, wherein the thermoplastic resin is polycarbonate or polymethylmethacrylate.
性樹脂成形物の製造方法において、板状熱可塑性樹脂成
形物に、表面を硬化させる薬剤を塗布する工程、粘着性
がなく、完全硬化に至らない状態まで、 前硬化させる
工程、引き続き、非平面を有する熱可塑性樹脂成形物に
成形する工程、該成形する工程後に、後硬化させる工程
を順次行うことを特徴とする表面を硬化させた非平面を
有する熱可塑性樹脂成形物の製造法。5. A method for producing a thermoplastic resin molded product having a non-flat surface-cured surface, the step of applying a surface-curing chemical agent to a plate-shaped thermoplastic resin molded product, complete curing without tackiness. The surface is cured by successively performing a pre-curing step, a step of molding into a thermoplastic resin molded product having a non-planar surface, and a post-curing step after the molding step until the state does not reach A method for producing a thermoplastic resin molded product having a non-planar surface.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4867491A JPH05220859A (en) | 1991-02-22 | 1991-02-22 | Surface-cured thermoplastic resin molding and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4867491A JPH05220859A (en) | 1991-02-22 | 1991-02-22 | Surface-cured thermoplastic resin molding and method for producing the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05220859A true JPH05220859A (en) | 1993-08-31 |
Family
ID=12809873
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4867491A Withdrawn JPH05220859A (en) | 1991-02-22 | 1991-02-22 | Surface-cured thermoplastic resin molding and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05220859A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004039856A1 (en) * | 2002-10-31 | 2004-05-13 | Kyoeisha Chemical Co.,Ltd. | Resin composition, transfer material and process for producing shaped item |
-
1991
- 1991-02-22 JP JP4867491A patent/JPH05220859A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004039856A1 (en) * | 2002-10-31 | 2004-05-13 | Kyoeisha Chemical Co.,Ltd. | Resin composition, transfer material and process for producing shaped item |
| JP4758647B2 (en) * | 2002-10-31 | 2011-08-31 | 共栄社化学株式会社 | Resin composition, transfer material and method for producing molded product |
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