JPS5926257A - Aromatic group polymer laminated shape - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an aromatic polymer laminate molded article having excellent adhesiveness and having a polyolefin as a surface layer and a styrene-based hydrocarbon graft copolymer-modified polyolefin as an intermediate adhesive layer.

Aromatic polymers such as polyethylene terephcrate, polycarbonate, and polyphenylene oxide are widely used in applications such as food containers, packaging materials, daily necessities, automobile parts, construction materials, and industrial machinery materials. Among these applications, in applications that require performance such as chemical resistance, water resistance, hot water resistance, and gas barrier properties, it is necessary to add properties to the aromatic polymer in order to impart these properties. Attempts have been made to laminate polyolefins such as polyethylene and polypropylene, but an adhesive with excellent adhesive performance has not yet been developed, and a laminate with excellent adhesiveness has not been obtained. Epoxy group-containing polyolefin, known as adhesive polyolefin,
Even if a laminate molded product of polyolefin and an aromatic polymer is formed as an intermediate adhesive layer, a laminate with good adhesiveness cannot be obtained, and attempts are made to directly laminate these modified polyolefins onto an aromatic polymer. However, similarly, a laminate molded product with excellent adhesiveness cannot be obtained.

The present inventors have found that when forming a laminate consisting of a polyolefin layer and an aromatic polymer layer, interposing a modified polyolefin with specific properties obtained by graft copolymerizing a styrene hydrocarbon as an intermediate adhesive layer results in improved adhesion. The inventors have discovered that a laminate molded product with excellent properties can be formed, and have arrived at the present invention. Furthermore, by forming the laminate of the present invention, it is possible to improve the water resistance, hot water resistance, and chemical resistance of the aromatic polymer, and it is also possible to impart gas barrier properties.

To summarize the present invention, the present invention provides a modified polyolefin in which (A) a surface layer made of a polyolefin, (B) a styrenic hydrocarbon is graft-copolymerized, and the grafting ratio of the styrenic hydrocarbon is a base polyolefin. 0.0% per 100 parts by weight.
The amount is in the range of 1 to 50 parts by weight, and the intrinsic viscosity [η] is 0.
．． 5 to 5 dl/g and whose crystallinity is in the range of 10% or more, an intermediate adhesive layer consisting of a styrene thread hydrocarbon graft copolymer modified polyolefin, and (C) a material other than a styrenic polymer. The gist is a base layer made of an aromatic polymer, and a laminate molded product made of the following.

The base layer (c) constituting the laminate molded product of the present invention is made of an aromatic polymer, and may be in any shape, including various shapes, sheets, films, etc. . Aromatic 1. fl (coalescence is an aromatic polymer other than a styrenic polymer containing a styrenic hydrocarbon component unit.More specifically, bisphenol A polycarbonate, bisphenol F polycarbonate, bisphenol AD polycarbonate, etc. Aromatic polycarbonate, polyphenylene oxide,
Polyphenylene oxide such as modified polyphenylene oxide, grafted polyphenylene oxide, etc.

Liethylene terephthalate, polybutylene terephthalate, polyethylene terephthalate iso-7 thalate, polyethylene 2,6-naphthalene dicarboxylate,
Examples include aromatic polyesters such as polyphenylene terephthalate, bisphenol A/terephthalic acid copolycondensate, and bisphenol A/terephthalic acid/isophthalic acid copolycondensate. These aromatic polymers may be foams. Among these aromatic polymers, polyethylene terephthalate, polycarbonate, polyphenylene oxide, and the like are preferably used in the laminate of the present invention.

The surface layer (A) constituting the laminate molded product of the present invention is a polyolefin layer. The polyolefins constituting the polyolefin layer include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-
Examples include homopolymers of α-olefins such as decene and 1-dodecene, or copolymers of two or more mixed components, and in addition to these components, vinyl acetate, acrylic esters, methacrylic esters, acrylic Vinyl monomers such as acid metal salts and methacrylic acid metal salts may be copolymerized. The base polyolefin may contain a diene component. The polyolefin constituting the surface layer is a crystalline polyolefin, and its crystallinity is usually in the range of 10% or more, preferably 15% or more. Also, its [η] is usually 0.5 to 5 dl/g,%
Preferably it is in the range of 0.7 to 4 dff/g. The thickness of the surface layer made of the polyolefin is arbitrary, but
Usually 5μ to 50mm, preferably 10μ to 40mm
It is in the range of mm.

Intermediate liquid if constituting the aromatic polymerization volume 1 of the present invention
Layer (B) is a modified polyolefin obtained by graft copolymerizing a styrene hydrocarbon onto a polyolefin. The base polyolefin (a) used for modification is ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4
-Methyl-1-pentene, 5-methyl-1-pentene,
Examples include homopolymers of α-olefins such as 1-octene and 1-decene, or copolymers of two or more mixed components, and the base polyolefin contains a trace amount, for example, 0.5 mol% or less. There is no problem even if the diene component is contained within a certain range. The base polyolefin has an intrinsic viscosity [
η] [value measured at 165°C in decalin solvent] is usually 0.5 to 5a[/g, preferably 0.7 to 4
dff/g, and the density is usually between 0.83 and 0.
．． 98 g 10n3, preferred, < Ha0.84 f
The crystallinity is usually 10% or more, preferably 15% or more.

The intermediate adhesive layer constituting the aromatic polymer laminate of the present invention (
The graft component (b) of the styrenic hydrocarbon graft copolymerized modified polyolefin of B) has the general formula [wherein R1,
R2 and R3 each represent a hydrogen atom or a lower alkyl group. ] This is a compound represented by in particular,
Styrene, α-methylstyrene, O-methylstyrene,
Examples include m-methylstyrene, p-methylstyrene, rl+-ethylstyrene, p-ethylstyrene, 0-isopropylstyrene, m-isopropylstyrene, and p-isopropylstyrene. Behind these styrenic hydrocarbon components, styrene, male-methylstyrene or p-methylstyrene components are preferred.

The grafting ratio of the styrenic hydrocarbon component of the styrenic hydrocarbon graft copolymerized modified polyolefin constituting the intermediate adhesive layer of the laminate molded product of the present invention is 0.1 to 0.1 to 100 M'L of the base polyolefin. It is necessary that the amount is in the range of 50 parts by weight, and more preferably in the range of 0.3 to 20 parts by weight. When the graft ratio of styrenic hydrocarbon is less than 0.1, the adhesive performance of the laminate molded product using the styrenic hydrocarbon graft copolymerized polyolefin is affected by the difference between the aromatic polymer layer and the intermediate adhesive layer. The adhesive strength decreases, and when the amount exceeds 50 parts by weight, the compatibility with the polyolefin decreases, resulting in a decrease in the adhesiveness with the polyolefin layer. Furthermore, the styrenic hydrocarbon graft copolymerized modified polyolefin has an intrinsic viscosity [η] of 0.5 to 5 dff.
/g and the crystallinity must be in the range of 10% or more, and furthermore, the intrinsic viscosity [η] must be 0.7
It is preferable that the crystallinity is in the range of 1 to 4 d#/g and the crystallinity is 15% or more.

Further, the density of the styrenic hydrocarbon graft copolymerized polyolefin is usually 0.83 to 0.98 g/
"J'% preferably 0.84 to 0.96 g/
C1n3 range, and its molecular weight distribution (MW/
in) is usually in the range of 1 to 20, preferably 1 to 10, and its melt viscosity at 230°C is preferably 10 to 5 x 106 voids, particularly preferably 5
It ranges from 0 to 8×105 voices. When the intrinsic viscosity [η] of the styrenic hydrocarbon graft copolymer-modified polyolefin becomes larger than 5 d 11 / g, the melt viscosity of the intermediate adhesive layer made of the styrenic hydrocarbon graft copolymer modified polyolefin becomes extremely large. The lamination moldability becomes poor, and as a result, the adhesion of the laminated molded product decreases.If it is less than 5 dβ/g, the melt viscosity is too low and it becomes difficult to mold it with a normal extruder.
Furthermore, even if the molding is done with excessive force, the strength of the intermediate adhesive layer is insufficient, resulting in a decrease in the adhesive strength of the laminated molded product. Furthermore, when the crystallinity of the styrenic hydrocarbon graph and the copolymerized modified polyolefin is less than 10%,
The adhesive strength of a laminate formed using the styrene-based hydrocarbon graft copolymer-modified polyolefin as an intermediate adhesive layer begins to decrease. The styrenic hydrocarbon graft copolymer-modified polyolefin may contain a by-product styrenic hydrocarbon homopolymer, but it is better to have a lower content of the styrenic hydrocarbon homopolymer. It is preferable that the adhesive performance of the laminate is improved. The proportion of the styrenic hydrocarbon homopolymer contained in the styrenic hydrocarbon graft copolymerized modified polyolefin is preferably 100 mol% or less based on the grafted styrene component units contained in the graft copolymerized modified polyolefin. , particularly preferably in a range of 50 mol% or less.

The styrenic hydrocarbon graft copolymer-modified polyolefin constituting the intermediate adhesive layer of the laminate molded product of the present invention can be produced by a conventionally known method. for example,
It is possible to adopt a method in which the base polyolefin (a) and the styrenic hydrocarbon (b) are reacted in a heated molten state, or a method in which they are reacted in a solution state.

The reaction may be carried out in the presence of a radical initiator, if necessary. As a radical initiator, organic peroxide,
Organic peresters such as benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(bermexybenzoate)hexyne-
3,1,4-bis(i;Qrt-butylperoxoisopropyl)benzene, lauroyl peroxide, ter
t-Butyl peracetate, 2,5-dimethyl-2,5
-di(tert-butylperoxy)hexyne-6,2
,5-dimethyl-2,5-di(tert-butylper1)
xy)hexane, tret-7'tyl perbenzoate, tart-butyl penof'-11 acetate, t
tert-butylperisobutyrate, tert-butylperu5eC-of-1ate, t,ert-butylperpivalate, cumylperpivalate and tert-butylperdiedylacetate, and other azo compounds such as azobisisobutyro Nitrile, dimethyl azoisobutylene
There is 1. Among these are dicumyl peroxide,
Di-tert-butylperoxide, 2,5-diethyl-2,5-di(tart-butylperoxy)hexyne-3,2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne, 1. 4-His (tert-
Dialkyl peroxides such as butylperoxyisopropyl)benzene are preferred. The temperature during the reaction is usually 7
0 to 350 °C.

Preferably it is in the range of 80 to 320°C.

In the laminate molded product of the present invention, the styrenic hydrocarbon graft copolymerized modified polyolefin is the intermediate adhesive layer (B
) to form. The thickness of the intermediate adhesive layer is arbitrary, but is usually in the range of 1 to 500μ, preferably 2 to 100μ. The styrenic hydrocarbon graft copolymer-modified polyolefin constituting the intermediate adhesive layer may be used as either a melt-type adhesive or a solution-type adhesive. Further, the intermediate adhesive layer may be composed only of the styrene-based hydrocarbon graft copolymer-modified polyolefin, but it is also possible to form a composition by adding other components to the extent that the adhesive performance is not impaired. do not have.

As a method for forming the laminate molded product of the present invention, for example, component polymers of each layer are separately supplied to six extruders,
Examples include a multilayer T-die sheet or multilayer film forming method in which molten polymers are joined together inside one die, and a tandem method in which molten polymers are thermally fused outside a die.

Next, the laminate molded product of the present invention will be specifically explained using Examples.

Example 1 Ethylene-propylene copolymer [ethylene content 80 mol%, intrinsic viscosity [η] 1.3 dl! /g, 100w/Mn2
．． 7. Styrene graft modified ethylene/propylene copolymer obtained by graft copolymerizing 2 parts by weight of styrene to 100 parts by weight [[1]] 1.4 d//g, crystallinity 14%, W /100n2,9, melt viscosity 3 x 10
5 Boise] in one extruder, and the resin temperature was 200°.
C was fed to a die for forming a three-layer composite 1-die sheet.

Separately, high-density polyethylene ([η] 1.5 cl/g) and polycarbonate [manufactured by Teijin Kasei Ltd., trade name: Panlyz, -125o] were each melted in separate extruders, and the resin temperature was adjusted to 200°C. 'C1280'C was supplied to the die, and the outer layer was a high-density polyethylene layer (50μ), the middle layer was a styrene-grafted modified ethylene-propylene copolymer layer (2011), and the inner layer was a polycarbonate layer (i m
A six-layer sheet consisting of m) was molded.

A test piece with a width of 16 m1η was cut from this 5-layer sheet,
By partially peeling off the polycarbonate and the styrene graft modified ethylene propylene copolymer, and then peeling the two-layer film side of the high density polyethylene and the styrene graft modified ethylene propylene copolymer 180 degrees, the polycarbonate and the styrene graft modified ethylene propylene copolymer are separated. The interlayer adhesion strength of the ethylene-propylene copolymer was measured.

As a result, the adhesive strength was 600 g/crn. Moreover, the bond between the high-density polyethylene and the styrene graft modified ethylene/propylene copolymer could not be separated, and the bond was sufficiently strong.

Examples 2 to 9 and Comparative Examples 1 to 5 Example 1 except that the ethylene-propylene copolymer shown in Table 1 was used as the base ethylene polymer for modification used in Example 1.
A three-layer laminate sheet was prepared in the same manner as above and evaluated in the same manner. The results are shown in Table 1.

Examples 10 to 13 A 6-layer laminate sheet was prepared in the same manner as in Example 1 except that the ethylene polymer shown in Table 2 was used as the base ethylene polymer for modification. Examples 14 to 16 Base for modification A propylene thread polymer shown in Table 2 was used as the polyolefin, and a propylene/ethylene random copolymer [ethylene content: 2 mol%, [η]] was used as the polyolefin that adhered to the styrene graft-modified propylene polymer as the base. A three-layer sheet was prepared in the same manner as in Example 1, except that sa6/g) was used.
The adhesive strength between polycarbonate and styrene graft modified propylene polymer was measured. The results are shown in Table 2.

Example 17 Styrene graft modified polybutene-1 shown in Table 2 was used as an adhesive with polycarbonate, and polybutene-1 [[η]s, od # /g':l
A three-layer sheet was prepared in the same manner as in Example 1, except that the adhesive strength of the three-layer sheet was measured. The results are shown in Table 2.

Example 1: Using styrene graft modified poly-4-methylpentene-1 shown in Table 2 as an adhesive with polycarbonate,
and the styrene graft modified poly 4-methylpentene-
4-methylpentene-1 (98 mol%)/decene-1 (2 mol%) copolymer [[η,) 2.5 dβ/g] was used as the polyolefin to be adhered to the styrene graft modified poly(4). A five-layer sheet was prepared in the same manner as in Example 1, except that the temperatures at which the -methylpentene-1 and 4-methylpentene-dodecene-1 copolymers were supplied to the die were each 260°C. The adhesive strength is shown in Table 2.

Example 19 As an adhesive layer that adheres to polycarbonate, a p-methylstyrene graft modified ethylene/propylene copolymer (
p-methylstyrene content 1.5 g/100 g
PE1Cη) 1.31? /g, and the base ethylene copolymer was the same as in Example 1.] A three-layer sheet was prepared in the same manner as in Example 1, except that the base ethylene copolymer was the same as in Example 1.

As a result, the adhesive strength with polycarbonate was 510g/
It was α.

Examples 10 and 21 As the aromatic resin, grafted polyphenylene oxide [manufactured by Asahi Vu Co., Ltd., trade name: Zylon 3011 V] and polyethylene terephthalate (Kanebo Co., Ltd. flu, EFG-6) tr were used instead of polycarbonate. :
Examples 22 and 26 The styrene graft modified ethylene propylene copolymer used in Example 1 and the same ethylene-propylene copolymer used as the modified base in Example 1 were mixed in an extruder at a ratio of 50,150 and 10/90. A five-layer sheet was prepared using the obtained styrene-modified ethylene-propylene copolymer composition in the same manner as in Example 1, and its interlayer adhesive strength was measured.

As a result, the adhesive strengths were 490g/α and 195g, respectively.
/(7).

Applicant: Mitsui Petrochemical Industries, Ltd. Agent Kazu Yamaguchi

Claims (1)

[Claims] (1) (A) A surface layer made of polyolefin,
(B) A modified polyolefin in which a styrenic hydrocarbon is graft copolymerized, wherein the grafting ratio of the styrenic hydrocarbon is in the range of 0.1 to 50 parts by weight based on 100 parts by weight of the base polyolefin, and the maximum viscosity〔
η] is in the range of 0.5 to 5 d (1/g,
an intermediate adhesive layer made of a styrenic hydrocarbon graft copolymer-modified polyolefin having a crystallinity of 10% or more, and (C) a base layer made of an aromatic polymer other than a styrenic polymer. Laminated molded body.