JPH11300912A - Coated poly 4-methyl-1-pentene resin molded product, heat insulating panel, and production thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a coated poly 4-methyl-1-pentene resin molded product excellent in heat insulating properties, heat resistance and mechanical strength, having good appearance free from coating irregularity and excellent in the adhesive strength of a coating film. SOLUTION: A coated poly 4-methyl-1-pentene resin molded product is constituted by providing a surface treatment agent layer formed from a surface treatment agent containing a modified aromatic ring-containing vinyl hydrocarbon/ conjugated diene copolymer or modified hydride obtained by the graft modification of an aromatic ring-containing vinyl hydrocarbon/conjugated diene copolymer or hydride thereof with an ethylenically unsaturated compd. on the surface of a molded product comprising a poly 4-methyl-1-pentene resin compsn. containing 50-95 wt.% poly 4-methyl-1-pentene, 0.1-10 wt.% modified poly 4- methyl-1-pentene subjected to graft modification by the ethylenically unsaturated compd. and 1-50 wt.% inorg. fiber and providing a coating film formed from a coating agent on the surface of the surface treatment agent layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to poly-4-methyl-
1-Pentene resin molded article A coated poly-4-methyl-1-pentene resin molded article having a coating film formed on its surface, particularly a coated poly4-methyl-1-pentene resin molded article which can be suitably used as a heat insulating panel And its manufacturing method.

[0002]

JP-A-59-120644 discloses poly-4-methyl-1-pentene, unsaturated carboxylic acid-modified poly-4-methyl-1-pentene, and glass fiber reinforced poly-4-methyl-pentene containing glass fiber. A 1-pentene resin composition is described, and JP-A-60-53549 discloses poly-4
-Methyl-1-pentene, unsaturated carboxylic acid-modified poly 4
An inorganic fiber reinforced poly-4-methyl-1-pentene resin composition comprising -methyl-1-pentene, nylon 66 and inorganic fibers is described.

[0003] Although these compositions have improved heat resistance and mechanical strength, the molded articles made of these compositions do not have sufficient surface coating performance. It is easy to occur, and a coated article with good appearance cannot be obtained. There is also a problem that a sufficient adhesive strength of the coating film cannot be obtained.

[0004] By the way, a heat insulating panel is used in a window frame portion of an aluminum sash, which is conventionally used. Such a window frame heat insulating panel has a low thermal conductivity, is excellent in heat insulation, and has a mechanical property. A coated molded article made of a glass fiber reinforced nylon resin composition having excellent strength is used. However, there is a problem that the coating performance changes with time because nylon has a hygroscopic property. Further, in order to save energy, there is a demand for a heat insulating panel having a smaller heat conductivity and excellent heat insulating properties.

As a resin having a lower thermal conductivity than nylon,
There are polypropylene and poly 4-methyl-1-pentene. However, polypropylene has insufficient heat resistance, and the baking temperature of the coating film is limited. On the other hand, poly-4-methyl-1-pentene has sufficient heat resistance, but has problems in coating performance and adhesion strength of the coating film as described above.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a coated poly-4 which is excellent in heat insulation, heat resistance and mechanical strength, has good appearance without coating unevenness, and has excellent adhesive strength of a coating film. An object of the present invention is to provide a methyl-1-pentene resin molded product and a heat insulating panel comprising the same. Another object of the present invention is to propose a manufacturing method capable of easily and efficiently manufacturing the coated poly-4-methyl-1-pentene resin molded article.

[0007]

The present invention provides the following coated poly-4
-Methyl-1-pentene resin molded article, heat insulation panel and manufacturing method. (1) Poly-4-methyl-1-pentene (A) 50-9
5% by weight, modified poly-4-methyl-1-pentene (B) graft-modified with an ethylenically unsaturated compound 0.1-1
An aromatic ring-containing vinyl hydrocarbon / conjugated diene copolymer is formed on the surface of a molded article comprising a poly-4-methyl-1-pentene resin composition [I] containing 0% by weight and 1 to 50% by weight of an inorganic fiber (C). Or a surface treatment agent (primer composition) [II] containing a modified aromatic ring-containing vinyl hydrocarbon / conjugated diene copolymer or a modified hydride (D) whose hydride is graft-modified with an ethylenically unsaturated compound. A coated poly-4-methyl-1-pentene resin molded article having a formed surface treatment agent layer (primer layer) and a coating film formed from a paint [III] on the surface of the surface treatment agent layer. (2) The modified aromatic ring-containing vinyl hydrocarbon / conjugated diene copolymer or modified hydride (D) is a styrene / (ethylene / butylene) / styrene block copolymer (SE)
The coated poly-4-methyl-1-pentene resin molded article according to the above (1), which is a maleic acid-modified product of BS). (3) The coated poly-4-methyl-1-pentene resin molded article according to the above (1) or (2), wherein the coating [III] is a powder coating. (4) A heat insulating panel comprising the coated poly-4-methyl-1-pentene resin molded product according to any one of the above (1) to (3). (5) Poly-4-methyl-1-pentene (A) 50-9
5% by weight, modified poly-4-methyl-1-pentene (B) graft-modified with an ethylenically unsaturated compound 0.1-1
An aromatic ring-containing vinyl hydrocarbon / conjugated diene copolymer is formed on the surface of a molded article comprising a poly-4-methyl-1-pentene resin composition [I] containing 0% by weight and 1 to 50% by weight of an inorganic fiber (C). Alternatively, a surface treatment agent [II] containing a modified aromatic ring-containing vinyl hydrocarbon-conjugated diene copolymer or a modified hydride (D) obtained by graft-modifying the hydride with an ethylenically unsaturated compound is applied to the surface treatment. Form an agent layer,
Next, a coating [III] is applied to the surface of the surface treatment agent layer, and then baked to form a coating film of poly-4-methyl-1.
-A method for producing a pentene resin molded product.

The poly (4-methyl-1-pentene) (A) used in the present invention is a homopolymer of 4-methyl-1-pentene or 4-methyl-1-pentene and usually not more than 15 mol%, preferably 9 mol%. % Or less of other α-olefins such as ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 1-tetradecene,
A copolymer with an α-olefin having 2 to 20 carbon atoms such as octadecene.

The poly-4-methyl-1-pentene (A) may be a melt flow rate (according to the test method of ASTM D1238, load 5.0 kg, temperature 260 ° C., MF
R) is 5 to 500 g / 10 min, preferably 2
It is desirable that the pressure is 5 to 150 g / 10 min. When the MFR is within the above range, a composition having excellent mechanical strength and moldability can be obtained.

[0010] The modified poly-4-methyl-1- used in the present invention
The pentene (B) is modified by graft copolymerization of an ethylenically unsaturated compound (F) to poly-4-methyl-1-pentene (hereinafter referred to as unmodified poly-4-methyl-1-pentene (E)). It is a graft modified product. The substrate structure of the modified product (B) is substantially linear, meaning that it does not have a three-dimensional crosslinked structure, which is confirmed by dissolving in an organic solvent such as p-xylene and by the absence of a gel. can do.

The unmodified poly-4-methyl-1-pentene (E) is a homopolymer of 4-methyl-1-pentene,
Or 4-methyl-1-pentene and usually another 15 mol% or less, preferably 9 mol% or less of other α having 2 to 20 carbon atoms.
-Copolymers with olefins. 2 to 20 carbon atoms
As the other α-olefin, the above-mentioned poly-4-methyl-
The same as those exemplified for 1-pentene (A) can be mentioned.

The poly-4-methyl-1-pentene (E) before modification has an intrinsic viscosity [η] of 0.5 to 25 dl / g, preferably 0.5 to 25 dl, measured at 135 ° C. in decahydronaphthalene. Those having 5 dl / g are preferred. When the intrinsic viscosity [η] is in the above range, the intrinsic viscosity of the modified product [η]
The preferred range described later is easily obtained.
The poly-4-methyl-1-pentene (E) before modification may be the same as or different from the poly-4-methyl-1-pentene (A).

As the ethylenically unsaturated compound (F), a polar monomer having an ethylenically unsaturated bond can be used. Specific ones, acrylic acid, unsaturated monocarboxylic acids such as methacrylic acid; maleic acid, fumaric acid, itaconic acid, citraconic acid, allyl succinic acid, mesaconic acid, glutaconic acid, nadic ^TM, methylnadic acid, tetrahydrophthalic phthalic acid, unsaturated dicarboxylic acids such as methyl hexahydrophthalic acid; maleic anhydride, itaconic anhydride, citraconic anhydride, allyl succinic anhydride, glutaconic acid, nadic acid ^TM, methylnadic anhydride, tetrahydrophthalic anhydride, Examples thereof include unsaturated dicarboxylic anhydrides such as methyltetrahydrophthalic anhydride, and a mixture of two or more of these components may be used. Among these ethylenically unsaturated compounds (F), maleic acid, maleic anhydride, nadic acid ^TM or nadic anhydride ^TM is preferred.

The amount of grafting of the ethylenically unsaturated compound (F) is 0.5 to 15% by weight, preferably 1 to 10% by weight. Here, the graft amount is the content of the structural unit derived from the graft monomer in the modified product. When the graft amount is in the above range, a composition having excellent heat deformation temperature, tensile strength, bending strength, impact strength and water resistance can be obtained.

Modified poly-4-methyl-1-pentene (B)
It is desirable that the intrinsic viscosity [η] measured in decahydronaphthalene at 135 ° C. is 0.5 to 10 dl / g, preferably 0.5 to 5 dl / g. When the intrinsic viscosity [η] is in the above range, heat deformation temperature, tensile strength,
A composition excellent in bending strength, impact strength and mechanical properties can be obtained.

The modified poly-4-methyl-1-pentene (B) has a molecular weight distribution (Mw / Mn) of 1 to 8,
Melting point 170-245 ° C, crystallinity 1-45%, DS
Those having a C parameter of 4 or less are preferred, and when these properties are in the above ranges, a composition having more excellent heat resistance and mechanical strength can be obtained. The molecular weight distribution is a value calculated from the weight average molecular weight (Mw) and the number average molecular weight (Mn) in terms of polystyrene measured by gel permeation chromatography using monodisperse polystyrene as a standard substance. The melting point is a value measured by a differential scanning calorimeter (DSC). Crystallinity is D
The melting area of the sample by SC (S), the melting area of indium as a control sample (So), and the melting energy (P) of the crystal part of poly-4-methyl-1-pentene (14)
1.7 J / g) and the melting energy of indium (Po)
(27 J / g) is a value obtained by the following equation. Crystallinity (%) = (S / So) × (Po / P) × 100 The DSC parameter is a value obtained by dividing the melting area (S) of the sample by DSC by the peak height at the melting point (that is, the maximum peak). Details of the method for measuring these physical properties are described in JP-B-3-30624.

Modified poly-4-methyl-1-pentene (B)
Can be produced by a known graft copolymerization method such as a solution method or a melt kneading method, but the solution method is preferred. As a specific method of the solution method, an ethylenically unsaturated compound (F) and a radical initiator are added in a solution of poly-4-methyl-1-pentene (E) in the presence of a solvent, and the mixture is heated. Examples of the method include graft copolymerization.

The proportion of the ethylenically unsaturated compound (F) used is usually 1 to 500 parts by weight, preferably 2 to 100 parts by weight, per 100 parts by weight of the poly-4-methyl-1-pentene (E).
It is desirable to use parts by weight. The usage ratio of the radical initiator is desirably 0.1 to 100 parts by weight, preferably 1 to 50 parts by weight based on 100 parts by weight of the poly-4-methyl-1-pentene (E). The proportion of the solvent used is poly 4-
10 to 100 parts by weight of methyl-1-pentene (E)
0-100,000 parts by weight, preferably 200-1000 parts by weight
It is desirably 0 parts by weight. The reaction temperature is usually 100 to
250 ° C, preferably 110-200 ° C, reaction time is 1
It is desirable to set it for 5 to 600 minutes, preferably 30 to 360 minutes.

Examples of the solvent used in the graft modification reaction include aliphatic hydrocarbons such as hexane, heptane, octane, decane, dodecane, tetradecane and kerosene; and methylcyclopentane, cyclohexane, methylcyclohexane, cyclooctane, cyclododecane and the like. Alicyclic hydrocarbons; benzene, toluene, xylene, ethylbenzene,
Aromatic hydrocarbons such as cumene, ethyltoluene, trimethylbenzene, cymene and diisopropylbenzene; chlorobenzene, bromobenzene, o-dichlorobenzene,
Carbon tetrachloride, trichloroethane, trichloroethylene,
Examples thereof include halogenated hydrocarbons such as tetrachloroethane and tetrachloroethylene. Of these, alkyl aromatic hydrocarbons are preferred.

Typical radical initiators used in the graft modification reaction are organic peroxides, and more specifically, alkyl peroxides, aryl peroxides, acyl peroxides, aroyl peroxides, ketone peroxides, peroxycarbonates, Peroxycarboxylate, hydroperoxide and the like can be mentioned. As the alkyl peroxide, diisopropyl peroxide, di-tert-butyl peroxide, 2,5-
Dimethyl-2,5-di-tert-butylperoxyhexine-3 and the like; aryl peroxides such as dicumyl peroxide; aryl peroxides such as dicumyl peroxide; acyl peroxides such as dilauroyl peroxide; aroyl peroxides; Examples of ketone peroxides such as dibenzoyl peroxide include methyl ethyl ketone hydroperoxide and cyclohexanone peroxide, and examples of hydroperoxides include tert-butyl hydroperoxide and cumene hydroperoxide. Among these, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di-tert-butylperoxyhexyne-
3, dicumyl peroxide, dibenzoyl peroxide and the like are preferred.

The inorganic fibers (C) used in the present invention include glass fibers, carbon fibers, boron fibers, potassium titanate fibers,
It is a fibrous substance composed of inorganic substances such as wollastonite and asbestos fibers. Further, the surface of the inorganic fiber is coated with a silane-based compound such as vinyltriethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, γ. -Surface treatment with glycidoxypropyltrimethoxysilane or the like may be performed.

In the present invention, poly 4 as a raw material of a molded article
The content of each component in the -methyl-1-pentene resin composition [I] is the same as that of the poly-4-methyl-1-pentene (A) 5.
0 to 95% by weight, preferably 60 to 90% by weight, the modified poly 4-methyl-1-pentene (B) 0.1 to 10% by weight, preferably 0.5 to 8% by weight, inorganic fiber (C) 1
５０50% by weight, preferably 5-40% by weight.

The poly-4-methyl-1-pentene resin composition [I] may contain a heat-resistant stabilizer, a weather-resistant stabilizer, a nucleating agent, a pigment, a dye, a lubricant, and rust as long as the object of the present invention is not impaired. Various compounding agents, such as inhibitors, which can be added to and mixed with ordinary polyolefins, can be compounded as other components.

The poly-4-methyl-1-pentene resin composition [I] comprises a Henschel mixer, a V-blender, a ribbon blender, and a tumbler blender. It can be prepared by a known method, such as a method of mixing by a method such as mixing with a single screw extruder, a twin screw extruder, or a kneader.

The poly-4-methyl-1-pentene resin composition [I] used in the present invention has low thermal conductivity and excellent heat insulation properties, and also has mechanical strength such as tensile strength, bending strength and impact strength, and Excellent heat resistance. In addition, when only inorganic fiber (C) is blended with poly-4-methyl-1-pentene (A), mechanical strength and heat resistance are improved, but modified poly-4-methyl-1-pentene (B) is further added. By blending, these properties are remarkably improved.

The modified aromatic ring-containing vinyl hydrocarbon / conjugated diene copolymer or modified hydride (D) used in the present invention
Is a method in which an ethylenically unsaturated compound (H) is graft-copolymerized on an aromatic ring-containing vinyl hydrocarbon / conjugated diene copolymer or a hydride thereof (hereinafter, referred to as a copolymer before modification or a hydride thereof (G)). Is a graft-modified product.

Examples of the copolymer before modification or its hydride (G) include styrene / butadiene / styrene triblock copolymer (SBS), which is a styrene / conjugated diene block copolymer, and styrene / butadiene block copolymer. Polymer (SBR), styrene / isoprene block copolymer, styrene / isoprene / styrene triblock copolymer (SIS), etc., and styrene / (ethylene / butylene) / styrene block copolymer which is a hydride of SBS (SEBS), and styrene / (ethylene / propylene) / styrene block copolymer (SEPS) which is a hydride of SIS. In these, SB
S, SIS and other styrene-conjugated diene-styrene triblock copolymers (G-1), SBR or hydrides thereof are preferred, and especially SBS, SEBS, SEPS,
SBR is preferred, and SEBS is particularly preferred.

The styrene / conjugated diene / styrene triblock copolymer (G-1) is a polymer block (S) which is a structural unit derived from at least one styrene in the molecule.
b) and a conjugated diene polymer block (Db), which is a structural unit derived from one or more conjugated dienes, for example, a copolymer represented by the following formula-(Sb-Db-Sb) n- (where n is an integer of 1 or more). Styrene, conjugated diene,
Examples of the conjugated diene constituting the styrene triblock copolymer (G-1) include isoprene and butadiene. These conjugated dienes may be used alone or in combination of two or more in the triblock copolymer.

The styrene-conjugated diene-styrene triblock copolymer (G-1) is described, for example, in US Pat. No. 3,265,765 or JP-A-61-192.
No. 743, etc., and the like. The hydrides of styrene / conjugated diene / styrene triblock copolymer (D-1) are described in, for example, JP-B-43-6636, JP-B-45-20504, and JP-B-48-3555. And those manufactured by a suitable method.

The styrene / conjugated diene / styrene triblock copolymer (G-1) or its hydride is obtained by adding tetrahydrofuran in view of the peel strength and the solid content of the coating film formed from the surface treating agent [II]. As a solvent, 40
The number average molecular weight measured by gel permeation chromatography at 1 ° C. is 1 × 10 ^{4 to} 1.8 × 10 ⁵ ,
Preferably, it is 1.5 × 10 ^{4 to} 1.2 × 10 ⁵ . The styrene content is desirably from 10 to 55% by weight, preferably from 15 to 50% by weight, from the viewpoints of peel strength, low-temperature characteristics, stickiness and the like of the coating film formed from the surface treating agent [II].

As the styrene / conjugated diene / styrene triblock copolymer (G-1) or its hydride, commercially available products can be used. Specifically,
Kraton TR-1101, TRKX which is a styrene-butadiene-styrene triblock copolymer (SBS)
-65S (both manufactured by Shell Chemical Co., Ltd.), styrene / isoprene / styrene triblock copolymer (SI
S) Clayton TR-1107, 1111, 11
12 (both made by Shell Chemical Co., Ltd.), hydrides of SBS Kraton G-1652, 1657 (both made by Shell Chemical Co., Ltd.), and SIS hydrides Septon 2002, 2007 (both made by Kuraray Co., Ltd.) And trade names).

Other commercial products of the copolymer (G) before modification include "Cariflex TR" (trademark, manufactured by Shell Chemical Co., Ltd.), "Solprene" (trademark, manufactured by Philips Petro Rifam), "Europrene SOLT"
(Trade name), "Tafprene" (trademark, manufactured by Asahi Kasei Corporation), "Sorprene-T" (trademark, manufactured by Nippon Elastomer Co., Ltd.), "JSRTR" (trademark, manufactured by Nippon Synthetic Rubber Company, Ltd.) STR "(trademark, manufactured by Denki Kagaku),
"Quintac" (trademark, manufactured by Nippon Zeon Co., Ltd.), "Clayton G" (trademark, manufactured by Shell Chemical Co., Ltd.), "Tuftec" (trademark, manufactured by Asahi Kasei Corporation) and the like can be mentioned. Examples of the hydride (G) of the copolymer before modification include S
"Kraton G1" which is a kind of EBS
650, G1701 "(trademark, manufactured by Shell Chemical Co., Ltd.),
"ToughTech" (trademark, manufactured by Asahi Kasei Corporation) and the like.

The SEBS is a thermoplastic elastomer comprising a polystyrene block unit and a polyethylene / polybutylene rubber block unit. In this styrene / (ethylene / butylene) / styrene block copolymer, a polystyrene block unit, which is a hard segment, exists as a bridge point of a rubber block unit to form a physical crosslink (domain). The rubber block unit existing between them is a soft segment and has rubber elasticity.

SEBS is disclosed, for example, in JP-B-60-5736.
It can be obtained by a known method described in No. 3 or the like. In the present invention, an aromatic ring-containing vinyl hydrocarbon / conjugated diene copolymer or a hydride thereof (G) before modification is used.
May be used in combination of two or more.

As the ethylenically unsaturated compound (H), the same compounds as the above-mentioned ethylenically unsaturated compound (F) can be used, and a mixture of two or more of these components may be used. As the component (H), maleic acid, maleic anhydride, acrylic acid, methacrylic acid, a half ester of maleic acid (for example, HOOCCH = CHCOOCH ₃ )
Are preferred.

The ethylenically unsaturated compound (H) will be described in more detail. Examples of the ethylenically unsaturated compound (H) include a hydroxyl group-containing ethylenically unsaturated compound,
It is possible to use amino group-containing ethylenically unsaturated compounds, epoxy group-containing ethylenically unsaturated compounds, unsaturated carboxylic acids and derivatives thereof, vinyl ester compounds, and polar monomers having an ethylenically unsaturated bond such as vinyl chloride. it can. Among these, a hydroxyl group-containing ethylenically unsaturated compound, an unsaturated carboxylic acid and a derivative thereof are preferable.

Examples of the hydroxyl group-containing ethylenically unsaturated compound include hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate,
-Hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxy-propyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, pentaerythryl mono (meth) Acrylate, trimethylolpropane mono (meth) acrylate, tetramethylolethane mono (meth) acrylate, butanediol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, 2- (6-hydroxyhexanoyloxy) ethyl acrylate, etc. (Meth) acrylic acid ester; other 10-undecene-1-ol, 1-octen-3-ol, 2-methanol norbornene, hydroxystyrene, N-methylolacrylamide, 2- (meth) - acryloyloxyethyl acid phosphate, glycerin monoallyl ether,
Examples include allyl alcohol, allyloxyethanol, 2-butene-1,4-diol, and glycerin monoalcohol.

Examples of the amino group-containing ethylenically unsaturated compound include vinyl monomers having at least one kind of amino group or substituted amino group represented by the following formula (1).

Embedded image (Wherein, R ¹ is a hydrogen atom, a methyl group or an ethyl group, and R ² is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, or 6 to 12 carbon atoms, preferably 6 to 8. The alkyl group and the cycloalkyl group may further have a substituent.)

Examples of such an amino group-containing ethylenically unsaturated compound include aminoethyl (meth) acrylate, propylaminoethyl (meth) acrylate, dimethylaminoethyl methacrylate, aminopropyl (meth) acrylate, and methacrylic acid. Alkyl ester derivatives of acrylic acid or methacrylic acid such as phenylaminoethyl acrylate and cyclohexylaminoethyl methacrylate; N
Vinylamine derivatives such as -vinyldiethylamine and N-acetylvinylamine; allylamine derivatives such as acrylamine, methacrylamine, N-methylacrylamine, N, N-dimethylacrylamide and N, N-dimethylaminopropylacrylamide; acrylamide And acrylamide derivatives such as N-methylacrylamide; p-aminohexylsuccinimide, 2-aminoethylsuccinimide and the like.

Examples of the epoxy group-containing ethylenically unsaturated compound include monomers having at least one polymerizable unsaturated bond group and at least one epoxy group in one molecule. Such epoxy group-containing ethylenically unsaturated compounds include, for example, glycidyl acrylate, glycidyl methacrylate, etc .; mono- and diglycidyl esters of maleic acid, mono- and diglycidyl esters of fumaric acid, mono- and diglycidyl esters of crotonic acid, tetrahydrogen Mono and diglycidyl esters of phthalic acid, mono and diglycidyl esters of itaconic acid, mono and diglycidyl esters of butenetricarboxylic acid, mono and diglycidyl esters of citraconic acid, endo-cis-bicyclo [2.2.1] hept -5
Mono- and diglycidyl esters of -ene-2,3-dicarboxylic acid (Nadic acid ^TM ), endo-cis-bicyclo [2.2.1] hept-5-en-2-methyl-2,3
Dicarboxylic acid mono- and diglycidyl esters such as dicarboxylic acid (methylnadic acid ^TM ) mono- and diglycidyl esters (alkyl groups having 1 to 12 carbon atoms in the case of monoglycidyl esters); and other alkylglycidyl p-styrenecarboxylic acids Ester, allyl glycidyl ether, 2-methylallyl glycidyl ether, styrene-p-glycidyl ether, 3,4-epoxy-1
-Butene, 3,4-epoxy-3-methyl-1-butene, 3,4-epoxy-1-pentene, 3,4-epoxy-3-methyl-1-pentene, 5,6-epoxy-1
-Hexene, vinylcyclohexene monoxide and the like.

Examples of the unsaturated carboxylic acids include acrylic acid, methacrylic acid, maleic acid, fumaric acid,
Tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, norbornene dicarboxylic acid, bicyclo [2,2,1] hept-2-ene-5,6
-Unsaturated carboxylic acids of dicarboxylic acids or derivatives thereof (eg acid anhydrides, acid halides, amides, imides,
Esters and the like).

Examples of the derivatives of the unsaturated carboxylic acids include, for example, maleenyl chloride, maleenyl imide, maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo [2.2.1] hept-2.
-Ene-5,6-dicarboxylic anhydride, dimethyl maleate, monomethyl maleate, diethyl maleate, diethyl fumarate, dimethyl itaconate, diethyl citrate, dimethyl tetrahydrophthalate, bicyclo [2.2.1] hept -2-ene-5,6-dicarboxylic acid dimethyl, hydroxyethyl (meth) acrylate,
Examples include hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, aminoethyl methacrylate, aminopropyl methacrylate, and the like.

Examples of the vinyl ester compound include vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate, vinyl versatate, vinyl laurate, vinyl stearate, and benzoic acid. Vinyl, vinyl salicylate, vinyl cyclohexanecarboxylate and the like can be mentioned.

The ethylenically unsaturated compound (H) can be used alone or in combination of two or more. The amount of the ethylenically unsaturated compound (H) grafted is 0.1 to 15% by weight, preferably 1 to 10% by weight.
It is desirable that

Various methods can be used as a method for graft copolymerizing the ethylenically unsaturated compound (H) to the copolymer before modification or its hydride (G). For example, a copolymer before modification or its hydride (G) is dissolved in an organic solvent, and the above ethylenically unsaturated compound (H) and a radical polymerization initiator are added thereto, followed by heating,
Stirring to carry out a graft copolymerization reaction; heating and melting the copolymer before modification or its hydride (G), and adding an ethylenically unsaturated compound (H) and a radical polymerization initiator to the obtained melt; A method of performing a graft copolymerization reaction by stirring; a copolymer before modification or a hydride thereof (G)
And a radical initiator, and the resulting mixture is supplied to an extruder and subjected to a graft copolymerization reaction while being heated and mixed; the copolymer before powder modification or its hydrogenated product (G) is ethylenically unsaturated. After impregnating with a solution obtained by dissolving a saturated compound (H) and a radical polymerization initiator in an organic solvent, the mixture is heated to a maximum temperature at which the powdery unmodified copolymer or its hydride (G) is not dissolved. And a method of graft copolymerization.

The reaction temperature is 50 ° C. or higher, especially 80 to 200
C is suitable, and the reaction time is about 2 to 10 hours.
The reaction system may be any of a batch system and a continuous system, but a batch system is preferable in order to uniformly perform the graft copolymerization.

When a graft reaction is carried out using a radical polymerization initiator, the radical polymerization initiator used is a reaction between a copolymer before modification or its hydride (G) and an ethylenically unsaturated compound (H). Any one may be used as long as it accelerates the reaction, but organic peroxides and organic peresters are particularly preferred. Specifically, benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (peroxybenzoate) hexyne-3,1,4-bis (tert) -Butylperoxyisopropyl) benzene, lauroyl peroxide, ter
t-butyl peracetate, 2,5-dimethyl-2,5
-Di (tert-butylperoxy) hexyne-3,
2,5-dimethyl-2,5-di (tert-butyl peroxide) hexane, tert-butylbenzoate,
tert-butyl perphenyl acetate, tert-
Butyl perisobutyrate, tert-butyl per-s
ec-octoate, tert-butyl perpivalate, cumyl perpivalate, tert-butyl perdiethyl acetate and the like. Other azo compounds, such as azobis-isobutylnitrile and dimethylazoisobutyl. Among these, dicumyl peroxide, di-tert-butyl peroxide,
2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, 1,4-bis (tert-butylperoxy) Dialkyl peroxides such as propyl) benzene are preferred. The radical polymerization initiator is preferably used in an amount of about 0.001 to 10 parts by weight based on 100 parts by weight.

When the graft reaction is carried out using an organic solvent, the organic solvent used is not particularly limited, but is, for example, an aromatic hydrocarbon such as benzene, toluene and xylene;
Aliphatic hydrocarbons such as hexane, heptane, octane and decane; alicyclic hydrocarbons such as cyclohexane, cyclohexene and methylcyclohexane; aliphatic alcohols such as ethanol and isopropanol; ketone solvents such as acetone, methyl isobutyl ketone and methyl ethyl ketone ;
Halogenated hydrocarbons such as trichloroethylene, racycloethylene, dichloroethylene, chlorobenzene and the like can be mentioned. Of these, aromatic hydrocarbons are preferred, and alkyl-substituted aromatic hydrocarbons are particularly preferred.
The organic solvent can be used alone or in combination of two or more.

In the present invention, the surface treatment agent [II] for forming the surface treatment layer is the modified aromatic ring-containing vinyl hydrocarbon.
It may consist of only the conjugated diene copolymer (D),
In an appropriate amount range that does not impair the object of the present invention, various stabilizers such as an antioxidant, a weather stabilizer, a heat inhibitor, an inorganic pigment, a coloring agent such as an organic pigment, carbon black, and ferrite, if necessary. Cadmium pigments such as titanium oxide, zinc white, lead white, lead red, cuprous oxide, red iron oxide, wet synthetic iron oxide, iron black, cadmium yellow, etc.
Even if other components such as molybdenum red, silver vermilion, graphite, zinc chromate, chromium oxide, navy blue, sedimentable barium sulfate, barite powder, ordinary light calcium carbonate, ultrafine calcium carbonate, alumina white, white carbon, etc. are blended Good. These can be used alone or in combination of two or more. Further, these other components may be directly dispersed in the surface treating agent, or may be mixed as a master batch.

Since the surface treating agent [II] is usually applied in a liquid form, it is mixed with a solvent. Specific examples thereof include aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as hexane, heptane, octane and decane; alicyclic hydrocarbons such as cyclohexane, cyclohexene and methylcyclohexane; Aliphatic alcohols such as isopropanol; ketone solvents such as acetone, methyl isobutyl ketone and methyl ethyl ketone; and halogenated hydrocarbons such as trichloroethylene, racycloethylene, dichloroethylene and chlorobenzene. The amount of the solvent to be used is not particularly limited, and may be blended so that the surface treating agent [II] has a viscosity that allows coating.
It is desirable to use 100 parts by weight, preferably 5 to 80 parts by weight.

The surface-treating agent layer formed from the surface-treating agent [II] used in the present invention has excellent adhesive strength with the poly-4-methyl-1-pentene resin composition [I]. In addition, since the surface treatment agent layer has excellent coating performance and little change in coating performance with time, the coating [III] can be uniformly applied so as not to cause uneven coating, and has a good appearance and high adhesive strength. The film can be easily formed.

The coating [III] used in the present invention is not particularly limited, and a known powder coating or solvent-type coating can be used, but a powder coating is preferable. Specific examples of the coating [III] include a solvent-type thermoplastic acrylic resin coating, a solvent-type thermosetting acrylic resin coating, an acrylic-modified alkyd resin coating, a polyester resin coating, an epoxy resin coating, an acrylic resin coating, and a polyurethane resin coating. And melamine resin paints.

The molded article of the coated poly-4-methyl-1-pentene resin of the present invention is prepared by applying the surface treating agent [II] to the surface of the molded article comprising the poly-4-methyl-1-pentene resin composition [I]. It is a coated article having a formed surface treatment agent layer and a coating film formed from the paint [III] on the surface of the surface treatment agent layer.

The shape of the molded article is not particularly limited.
Any shape such as a prismatic shape can be used. The surface treatment agent layer is preferably formed on the entire surface of the molded article.
The thickness of the surface treatment agent layer is 1 to 20 μm, preferably 2 to 1 μm.
It is desirable that the thickness be 5 μm. It is preferable that the coating film is also formed on the entire surface of the molded article. The coating thickness is 5-100μ
m, preferably 20 to 60 μm.

In order to produce the coated poly-4-methyl-1-pentene resin molded article of the present invention, first, a molded article is molded from the above-mentioned poly-4-methyl-1-pentene resin composition [I]. The molding method is not particularly limited, and a known molding method capable of molding a molded article having a desired shape can be employed. For example, methods such as compression molding, transfer molding, injection molding, and extrusion molding can be employed.

Next, the surface treatment agent [II] is applied to the surface of the molded article molded as described above to form a surface treatment agent layer. The application method is not particularly limited, and a method such as brushing, spraying, a roll coater, and a dipping method can be employed. The surface treatment layer can be formed by evaporating the solvent from the applied surface treatment agent [II].

Next, the paint [III] is applied to the surface of the surface treatment agent layer formed as described above, and baked to form a coating film (cured coating film). The method of applying the paint [III] can be selected according to the paint to be used. In the case of a powder paint, the paint can be applied by a known method such as an electrostatic coating method. In the case of solvent type paint,
Methods such as brushing, spraying, a roll coater, and a dipping method can be employed. The applied paint [III] is usually baked at 50 to 200 ° C, preferably 100 to 200 ° C to form a coating film. The baking method is not particularly limited, and a normal method of heating with a nichrome wire, infrared rays, high frequency, or the like can be employed, and is appropriately selected depending on the material and shape of the molded product, the properties of the paint to be used, and the like.

In the present invention, since the surface treatment agent layer is formed on the surface of the molded article, the coating [III] can be applied uniformly without causing unevenness in coating, and a coated molded article having a good appearance can be obtained. be able to. Further, the surface treatment agent layer does not absorb moisture, has excellent coating performance, and its performance does not change with time, so that the coating [III] can be applied efficiently. The surface treatment agent layer is made of poly 4-methyl-
Since the adhesive strength to both the 1-pentene resin composition [I] and the coating film is excellent, a coating film having a high adhesive strength to a molded article comprising the poly-4-methyl-1-pentene resin composition [I] Can be formed. Furthermore, since the poly-4-methyl-1-pentene resin composition [I] and the surface treatment agent [II] are excellent in heat resistance, the coating [II]
Even if I) is baked, there are no problems such as deformation of the molded product or reduction in the adhesive strength.

The coated poly-4-methyl-1-pentene resin molded article of the present invention can be used in fields where heat insulation, mechanical strength and appearance are required, but it is preferable to use it as a heat insulation panel. In particular, it can be suitably used as a window frame heat insulating panel.

[0060]

According to the present invention, a coated poly-4-methyl-1-pentene resin molded article is obtained by forming a modified aromatic ring-containing vinyl hydrocarbon / conjugate on the surface of a molded article made of a poly-4-methyl-1-pentene resin composition. Since it has a surface treatment agent layer formed from a surface treatment agent containing a diene copolymer or a modified hydride, and further has a coating film formed from a paint on its surface, heat insulation, heat resistance and mechanical strength are improved. It is excellent, has good appearance without uneven coating, and has excellent adhesive strength of the coating film. The heat-insulating panel of the present invention has the above-mentioned coated poly 4-methyl-
Since it is made of a 1-pentene resin molded product, it exhibits excellent heat insulating properties and has a good appearance, so that it can be suitably used particularly as a window frame heat insulating panel. The method for producing a coated poly-4-methyl-1-pentene resin molded product of the present invention comprises applying a surface treatment agent containing a modified aromatic ring-containing vinyl hydrocarbon / conjugated diene copolymer to the surface of the molded product. After forming the layer, a coating film is formed on the surface thereof, so that the surface treatment agent layer improves the coatability, and the coated poly-4-methyl-1-pentene resin molded product can be easily and efficiently manufactured. .

[0061]

Next, an embodiment of the present invention will be described. Production Example 1 4-methyl-1-pentene homopolymer (intrinsic viscosity [η]
= 1.7 dl / g, Mw / Mn = 7.5, melting point = 241
° C, crystallinity = 42%) in toluene solvent.
A graft reaction of maleic anhydride was performed at 5 ° C. with a dicumyl peroxide catalyst. A large excess of acetone was added to the obtained reaction product to precipitate a polymer, which was collected by filtration. The precipitate was repeatedly washed with acetone to obtain a maleic anhydride graft-modified poly-4-methyl-1.
-A pentene was obtained.

Example 1 10 parts by weight of glass fiber was added to 99 parts by weight of the unmodified 4-methyl-1-pentene homopolymer used in Preparation Example 1, and maleic anhydride graft-modified poly 4 prepared in Preparation Example 1 was used. −
1 part by weight of methyl-1-pentene was added, and after mixing the three components, the mixture was granulated by a usual extruder to obtain pellets. A test piece was prepared from the pellet using an injection molding machine, and a bending test, a tensile test, an Izod impact test, a thermal deformation test, and a thermal conductivity test were performed. The results shown in Table 1 were obtained.

Examples 2 and 3 and Comparative Examples 1 and 2 Except that 4-methyl-1-pentene homopolymer, modified poly-4-methyl-1-pentene and glass fiber were used in the proportions shown in Table 1, The test was performed in the same manner as in Example 1. The results are shown in Tables 1 and 2.

[0064]

[Table 1]

[0065]

[Table 2]

Notes to Tables 1 and 2 * 1 Graft-modified product: Maleic anhydride-grafted poly-4-methyl-1-pentene * 2 Flexural strength: ASTM D 790 * 3 Tensile strength: ASTM D 638 * 4 Izod impact strength : ASTM D 256 * 5 Thermal deformation temperature: ASTM D 648, load 264
psi * 6 Thermal conductivity: BS 874A

Example 4 In a 1.0 liter autoclave equipped with a stirrer, Kraton G-1652 (hydrogenated styrene / butadiene / styrene triblock copolymer; Shell Chemical Co., number average molecular weight: (88,000, styrene content: 30% by weight) and 400 ml of toluene were charged, and the temperature was raised to 165 ° C. with stirring. About 20 g of maleic anhydride and 7.1 g of di-t-butyl peroxide
Are added in 4 hours each, and then another 16 hours
Stirred at 5 ° C for 2 hours. In the modified hydride synthesized in this manner, the graft amount of maleic anhydride was 4.4.
The solution viscosity was 600 mPa · s as measured by an E-type viscometer after being adjusted to a solid concentration of 20% by weight by dilution with toluene.

To 150 g of the above solution, 285 g of methylcyclohexane, a conductive masterbatch (Unistol P-4010D manufactured by Mitsui Chemicals, Inc., trademark, pigment concentration 17%)
20 g was added to obtain a surface treating agent. Next, the surface treatment agent was applied to the test piece prepared in Example 3 by a spray gun so as to have a film thickness of 5 μm.
-287, manufactured by Nippon Bee Chemical Co., Ltd.) to a thickness of 35 μm. After 10 minutes at room temperature, 80 ° C,
Baking was performed for 45 minutes.

Using this as a sample, the adhesion of the coating film was evaluated by a grid test according to the following method, and it was 100/100. << Cross-cut test >> The surface of the painted test piece is JIS K5
According to the cross-cut test method described in No. 400, a test piece was prepared by cross-cutting, and an adhesive tape (Nichiban Co., Ltd., cellophane tape) was attached on the cross-section of the test piece. This was quickly pulled in the direction of 90 ° to be peeled off, and the number of grids that were not peeled out of the 100 grids was counted and used as an index of adhesion.

Claims (5)

[Claims] 1. Poly-4-methyl-1-pentene (A) 5
0-95% by weight, modified poly-4-methyl-1-pentene (B) graft-modified with an ethylenically unsaturated compound.
An aromatic ring-containing vinyl hydrocarbon / conjugated diene is formed on the surface of a molded article comprising a poly-4-methyl-1-pentene resin composition [I] containing 1 to 10% by weight and 1 to 50% by weight of an inorganic fiber (C). The polymer or its hydride is formed from a surface-treating agent [II] containing a modified aromatic ring-containing vinyl hydrocarbon / conjugated diene copolymer graft-modified with an ethylenically unsaturated compound or a modified hydride (D) A coated poly-4-methyl-1-pentene resin molded article having a surface treatment agent layer and a coating film formed from the coating material [III] on the surface of the surface treatment agent layer. 2. The modified aromatic ring-containing vinyl hydrocarbon / conjugated diene copolymer or modified hydride (D) is a maleic acid-modified styrene / (ethylene / butylene) / styrene block copolymer (SEBS). The coated poly (4-methyl-1-pentene) resin molded article according to claim 1. 3. The paint [III] is a powder paint.
Or a coated poly-4-methyl-1-pentene resin molded product according to item 2. 4. A heat insulating panel comprising the coated poly-4-methyl-1-pentene resin molded product according to claim 1. 5. Poly-4-methyl-1-pentene (A) 5
0-95% by weight, modified poly-4-methyl-1-pentene (B) graft-modified with an ethylenically unsaturated compound.
An aromatic ring-containing vinyl hydrocarbon / conjugated diene is formed on the surface of a molded article comprising a poly-4-methyl-1-pentene resin composition [I] containing 1 to 10% by weight and 1 to 50% by weight of an inorganic fiber (C). Applying a surface treating agent [II] containing a modified aromatic ring-containing vinyl hydrocarbon / conjugated diene copolymer or modified hydride (D) in which the polymer or its hydride is graft-modified with an ethylenically unsaturated compound; A method for producing a coated poly (4-methyl-1-pentene) resin article, comprising forming a surface treatment agent layer, applying a paint [III] on the surface of the surface treatment agent layer, and baking to form a coating film.