JPS5929160A - Aromatic group resin 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 resin laminate molded article having excellent adhesive properties and having a polyolefin as a surface layer and a modified polyolefin grafted with an unsaturated dicarboxylic acid or its anhydride as an intermediate adhesive layer. .

Aromatic M 2 -based resins such as polyethylene terephthalate, 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. For these applications, it is particularly resistant to chemicals, water, hot water, and il.
In applications that require performance such as fl basher properties, attempts have been made to laminate polyolefins such as polyethylene and polypropylene onto the aromatic resin in order to impart these properties. No adhesive has been developed yet, and a laminate with excellent adhesiveness has not yet been obtained. For example, even if a laminate of polyolefin and aromatic resin is formed using an epoxy group-containing polyolefin, which is known as ordinary adhesive polyolefin, as an intermediate adhesive layer, a laminate with good adhesiveness cannot be obtained. , kneading aromatic resin 11. However, even if you try to directly laminate the resin, you will not be able to produce a laminate molded product that has excellent adhesive properties.

When forming a laminate consisting of a polyrefin layer and an aromatic resin layer, the present inventors have developed a modified polyreflex resin having the properties of 'Fat', which is obtained by graft copolymerizing an unsaturated dicarboxylic acid or its anhydride. It has been discovered that a laminate molded product with excellent adhesiveness can be formed by interposing the compound as an intermediate adhesive layer, and the present invention has been achieved based on this discovery. Furthermore, by forming the laminate of the present invention, the water resistance, hot water resistance, and chemical resistance of the 1'7y aromatic resin can be improved.

To summarize the present invention, the present invention is a modified polyolefin in which (A) a surface layer consisting of boIJ, 4refine, and (13) a small saturated dicarboxylic acid or its anhydride is graft copolymerized,
The grafting ratio of dicarboxylic acid or its anhydride is OJI + for the base polyolefin 1 (]
Intrinsic viscosity rη] is 0.5.
to 5d1/g and its crystallinity is 10
A laminate molded product comprising: an intermediate adhesive JM made of a graft copolymer of an unsaturated dicarboxylic acid or its anhydride in a range of 65% to 65%; and (0) a base layer made of an aromatic resin. There is a paper C whose gist is .

The base layer (C) constituting the laminate molded product of the present invention (1η) is
It is made of aromatic resin and can be in any shape, including various shapes, sheets, films, etc. The aromatic resin is an aromatic resin other than a styrene polymer containing a moderate amount of styrene hydrocarbon component. More specifically, polycarbonate of bisphenol, polycarbonate of bisphenol Ii', aromatic polycarbonate such as polycarbonate of bisphenol A and D, polyphenylene]oxide, modified t'J :Polyphenylene oxide 1 such as polyphenylene oxide and grafted polyphenylene A oxide
-cyto, polyethylene prephthalate, polybutylene terephthalate, polyethylene tere7thalate/isophthalate, polyethylene/2,6-naphthalene dicarboxylate, polyethylene prephthalate, bisphenol A/terephthalic acid copolycondensate, bisphenol A/terephthalic acid - Aromatic polyesters such as isophthalic acid copolycondensates can be exemplified. These aromatic resins may be foams. Among these aromatic resins, it is preferable to use polyethylene prephthalate, borino-novo nitrate, or polyethylene phthalate in the laminate of the present invention.

The surface layer (A+ is a polyolefin layer) constituting the laminate molded product of the present invention. Examples of the polysubrefin constituting the polyolefin layer include ethylene, propylene, 1-butene, 1-pentene, 1-hegyin, 4 -Methyl-1-pentene, ro-methyl-1-pentene, 1-octene, 1-
Examples include monopolymers of α-olefins such as decene and 1-dodecene, or copolymers of two or more mixed components.In addition to these components, vinyl acetate, acrylic esters, and methacrylic acid Vinyl intermediates such as esters, acrylic M metal salts, and methacrylic acid metal salts may be copolymerized. Even if the base bottle IJ7) contains a diene component, it will not hold up. The polyolefin constituting the surface area is polyolefin.
Its crystallinity is usually 10% or more - 1-1 preferably 15%
It is within the range of 2. Moreover, the [η] is usually in the range of 0.5 to 5 cl (1/g1, preferably (), 7 to 4 dl/g).

The thickness of the surface layer is arbitrary, but usually 5// to 53
mm, preferably in the range of 10/l to 4 Qmm.

Intermediate adhesive m (
B) is a modified Fl:bo IJ obtained by graft copolymerizing anhydride of unsaturated dicarbonate (?Lt) to polysubrefin,
1' L-fin. The base polyrefin (8) used for modification is ethylene, propylene, 1-butene, 1
-Pentene, 1-hexane, 4-meguru-1-butene, methyl-1-pentene, 1-kariten, 1-
Homopolymers of α-olefins such as decene or copolymers of mixed components of ``2'' can be exemplified;
There is no problem even if the diene component is contained within the range of mol % or less. The base polyurethane resin has an intrinsic viscosity of C1 (
d, e/gz is preferably 0.
．． 7 to 4dj7/g, and the density is usually 0.
The crystallinity is usually in the range of 10 to 65%, preferably in the range of 15 to 60%. be.

Intermediate layer (I) constituting the aromatic resin laminate of the present invention
Examples of the graft component (b) of the modified polyrefin grafted with an unsaturated dicarboxylic acid or anhydride thereof include maleic acid, fumaric acid, itaconic acid, citraconic acid, lucosuccinic acid, methaconic acid, and glutamonic acid. , unsaturated dicarboxylic acids such as nadic acid, methylnadic acid, tetrahydrophthalic acid, methylhydrofucuric acid, maleic anhydride, itaconic anhydride, citraconic anhydride,
Examples include anhydrides of unsaturated dicarboxylic acids such as allylsuccinic anhydride, glutaconic anhydride, nadic anhydride, methyl nadic anhydride, sulfur detrahydroheptalic acid, and methyltetrahydrophthalic anhydride. Mixed components are also acceptable. Among these unsaturated dicarboxylic acids or anhydrides thereof, maleic acid, maleic anhydride, nadic acid, or nadic anhydride is preferably used. Also, among these,
Maleic anhydride is particularly preferred.

The grafting ratio of the unsaturated dicarboxylic acid component or its anhydride component of the modified polyolefin grafted with the unsaturated dicarboxylic acid or its anhydride in the aromatic 4TJF adhesive of the present invention is 100 parts by weight of the base polyolefin. It is necessary that R=J t, be in the range of 0.01 to 5 parts by weight, and more preferably in the range of [10 5 to 3 parts by weight. When the grafting proportion of the unsaturated dicarboxylic acid or its anhydride component is less than 0.01 parts by weight or greater than 5 parts by weight, the grafting proportion of the unsaturated dicarboxylic acid or its anhydride component is
The adhesive strength between the binder made of Mibori-Kari Refin and the aromatic resin layer is low.

Further, the unsaturated dicarboxylic acid or G's anhydride graft copolymerization modified 1/1:polytone reflex has an intrinsic viscosity [η] of I. It is necessary that the crystallinity is in the range of 5 to 5 (1. l/g and the crystallinity is in the range of 10 fl to 65%, and the intrinsic viscosity [η] is 0.7 to / lde/g and crystallinity of 15 to 6
Preferably, it is in the range of 0%. In addition, the density of the saturated dicarboxylic acid or its anhydride graft copolymerized modified polyester resin is usually 0.83.
l. 9 fl glo, preferably [], is in the range of ε14 to 0.93 g/Cnol13, and its molecular weight distribution (MW/M11) is usually 1 to 15,
It is preferably in the range of 1 to 10, and its 230'C
The melt viscosity at is preferably in the range from 10 to 5×10 6 voids, particularly preferably from 50 to 8×10 5 voids. The intrinsic viscosity [η] of the unsaturated dicarboxylic acid or its anhydride graft copolymerized modified poly”refin is 5.
When it is larger than dβ/g, the FV Tt agent made of the unsaturated dicarboxylic acid or its anhydride graft copolymerized modified 1r1, poly-refin has a very thick melt viscosity of 4V, so that lamination molding f'l is required.

becomes defective and is smaller than 11.5 cle/g'/"
As a result, the melt viscosity decreases, making it difficult to mold using an ordinary extruder.
< /+: Also, even if the molding is done with force, the strength of the adhesive is insufficient, so the adhesive strength becomes low. Furthermore, the degree of crystallinity of the unsaturated dicarboxylic acid or its anhydride graft copolymerized polyolefin is 10.
%, the performance of the adhesive made of the unsaturated dicarboxylic acid or its anhydride graft copolymer modified P1: deformed resin is such that the adhesive strength decreases due to insufficient adhesive strength.

The adhesive for aromatic resins of the present invention may be composed only of the unsaturated dicarboxylic acid or its anhydride graft copolymer-modified polyolefin, but other components may be added to the composition as long as the adhesive performance is not impaired. It can't be helped because it forms things.

The unsaturated dicarboxylic acid or its anhydride graft copolymerization-modified polyolefin, which is the adhesive for aromatic resins of the present invention, can be produced by a conventionally known method.

For example, a method may be adopted in which the base polyolefin (a,) and the unsaturated dicarboxylic acid or its anhydride (b) are reacted in a heated molten state, or a method may be adopted in which the base polyolefin (a,) is reacted in a solution state. The C1 reaction may be carried out in the presence of a radical initiator, if necessary.

Examples of radical initiators include organic peroxides, organic esters, such as penzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, and
rt-butylvermegisito, 2,5-dimethyl-2,5
-di(peroxide benzoate)hekisinro, 1
, 4-hys(7 ert, -) tyruvel, gisoisoprobil) benzene, lauroyl periohe-side, ter
t-Butylberacetate, 2,5-dimedyl-2,5
-di(7 ert-)chill level 4th)hexyne-
6,2,5-dimethyl-2,5-di(tert-butylperoxy)hexin, tert-butylberbenzoate, tert-butyl/L/H/L/phenylacetate, tert-butylberisobutyrate ,ter
t-butyl peru 5ec-mectoe 1., tert
-butylberbivalate, cumylberbivalate and tθr1. - butylverdiedylacetate and other azo compounds such as azobisisobutyronitrile and dimylylazoisobutyrate. Among these are dicumyl peroxide, di-bert-butylber-peroxide,
2,5-dimethyl-2,5-di(tert-butylvermexy)hexyne-5,2,5-dimethyl-2,5-di(tert-butylperoxy)hegysan, 1,4-bis('t, Dialkyl peroxides such as Qrt-butylperoxyisopropyl)benzene are preferred. The temperature during the reaction is usually 70 to 350'C, preferably 80'C.
It ranges from 0 to 320'C.

In the laminate molded product of the present invention, the unsaturated dicarboxylic acid or its anhydride graft copolymerized unsaturated polyolefin forms the intermediate adhesive layer CB). Although the thickness of the intermediate adhesive layer is arbitrary, it is usually 1 to 5 D Ott%.
Preferably it is in the range of 2 to 100 zl.

The unsaturated dicarboxylic acid or its anhydride graft copolymerized 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 unsaturated dicarboxylic acid or its anhydride graft copolymer-modified polyolefin, but other components may be added to form a composition within a range that does not impair adhesive performance. It's okay to stay.

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 multi-NT 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 heat-sealed outside the die.

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

Example 1 Ethylene-propylene copolymer C Ethylene content 80 mol%, intrinsic viscosity [η) 1.3647 g (Mw/πn
) 2.7, crystallinity 15%] Maleic anhydride graft-modified ethylene e-propylene copolymer CC obtained by graft copolymerizing 0.5 parts by weight of maleic anhydride to 100 parts by weight.
η〕1. /I d6/g, crystallinity 14%, (MW
/in) 5.1, melt viscosity 5.5 X I C1
5 Boise] in one extruder, and the resin temperature was 200.
'C' was fed into a die for forming a 5-layer composite 'l'-die sheet. Separately, high-density polyethylene [[η] 1.5d4/g and polycarbonate [manufactured by Kijin Kasei Co., Ltd., trade name Panlite L-125DJ] were melted in separate extruders, and the resin temperatures were adjusted to 200"C and 250"C, respectively. The mixture was supplied to the die at °C, and the outer layer was a high-density polyethylene layer (50 Il), the middle layer was a maleic anhydride graft modified ethylene-propylene copolymer layer (201z), and the inner layer was a polycarbonate layer (1 mm). A layered sheet was created.

A test piece with a width of iQmm was cut from this three-layer sheet, and the gap between the polycarbonate and the maleic anhydride graft-modified ethylene-propylene copolymer was partially peeled off, and the gap between the high-density polyethylene and the maleic anhydride-grafted modified ethylene-propylene copolymer was separated. The interlayer adhesive strength between the polycarbonate and the maleic anhydride graft-modified 1/2-propylene copolymer was measured by peeling the two-layer film side 180 degrees.

As a result, the adhesive strength was 65 IT g/rru. In addition, the adhesive between the high-density polyethylene and the anhydrous macer/inic acid graft modified V1: ethylene/propylene copolymer was sufficiently strong and could not be peeled off. 1, Examples 2 to 7, and Comparative Example 1 to 7 A 6-layer laminated sheet was prepared in the same manner as in 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, and evaluated. The results are shown in Table 1.

Examples 8 to 10 Six-layer laminate sheets were prepared in the same manner as in Example 1, except that the ethylene polymers shown in Table 2 were used as the ethylene polymers for modification.

The results are shown in Table 2.

Examples 11 to 1 Modified 'I'1' 1 As the base polyolefin, a propylene thread polymer not shown in Table 2 was used, and as the polyolefin that adhered to the maleic anhydride graft-modified propylene polymer of the base, propylene thread polymer was used. Edilenone random copolymer [ethylene content 2 mol%, [η] 2.5 dn/g
) A three-layer sheet was prepared in the same manner as in Example 1, and the adhesive strength between the polycarbonate and the water-maleic acid graft-modified propylene polymer was measured.

The results are shown in Table 2.

Example 14 Maleic anhydride graft-modified polybutene-1 shown in Table 2 was used as an adhesive with polycarbonate, and polybutene-1 [[η]] was used as a polyolefin to adhere to the maleic anhydride graft-modified polybutene-1. Od
A 3FvI sheet was prepared in the same manner as in Example 1, except that (1!/g:) was used, and its adhesive strength was measured. The results are shown in Table 2.

Example 15 Maleic anhydride graft-modified poly(4-methylpentene-1) shown in Table 2 was used as the λ′1 agent for polycarbonate, and the maleic anhydride-grafted poly(4-methylpentene-1)
-4-methylpentene-1 (98 mol%) and decene-1 (
2 mol %) copolymer [[η,: 12.5 dβ/g], the maleic anhydride-grafted poly-4-medylpendene-1 and 4-mablepentene-7-1 copolymer was added to da.r. A 95-layer sheet was prepared in the same manner as in Example 1, except that the supply temperature was 260"C, and the adhesive strength thereof is shown in Table 2.

Example 16 As an adhesive layer that adheres to polycarbonate, a nadic anhydride-grafted modified ethylene-propylene copolymer (nadic anhydride-containing fN [1,2 g / 10 (] g -
PE, [η) 10. Example 1 except that 1 d l/F, % base ethylene copolymer is the same as Example 1)
A filter layer sheet was prepared in the same manner as above.

As a result, the adhesion strength with polycarbonate was 7) 40 w/cm.

Examples 20 and 21 As the aromatic resin, grafted polyphenylene oxide (manufactured by Asahi Dow Co., Ltd., trade name: Zylon 300V) and polyethylene terephthalate (Kanebo Co., Ltd., EFG-6) were used instead of polycarbonate. Filter layer sheets were prepared in the same manner as in Example 1 except that the temperatures were 20°C and 270°C, respectively. As a result, the delamination strength was II 80 g/CH+, 630 g, respectively.
/cnl.

Examples 22 and 2 The maleic anhydride graft-modified ethylene-propylene copolymer used in Example 2 and the ethylene-propylene copolymer used as the base for modification in Example 1 were mixed with 50150 and 10/90. They were mixed in an extruder in the following proportions. Using the obtained maleic anhydride-modified ethylene-propylene copolymer composition, a six-layer sheet was prepared by the same method G as in Example 1, and the interlayer adhesive strength was measured. As a result, the adhesive strengths were 490 g/crl and 195 g/on, respectively. .

Applicant: 3J1 Sekiyoshi Chemical Subaru Co., Ltd. (Person)
Kazu Yamaguchi

Claims (1)

[Claims] (1) (A) Surface layer consisting of poly secondary reflex,
(B) A modified polyrefin grafted with an unsaturated dicarboxylic acid or its anhydride, wherein the grafting ratio of the unsaturated dicarboxylic acid or its anhydride is 0.01 to 5 parts by weight based on 100 parts by weight of the base polyolefin. The intrinsic viscosity [η] is in the range of 0.5 to 5 a
5/g and its crystallinity is between 5 and 6.
5% and its molecular weight distribution (uw/ran
) is in the range of 1 to 15, an intermediate adhesive layer made of a modified polyolefin grafted with an unsaturated dicarboxylic acid or its anhydride, and (C) a base layer made of an aromatic resin.