JPS5925856A - Adhesive for aromatic polymer - Google Patents

Abstract

PURPOSE:To obtain titled adhesives for coating on containers and/or packaging materials for foods, capable of giving high bonding strength in laminating an aromatic polymer layer on a polyolefin one, by carrying out a graft copolymerization of a styrene hydrocarbon to a specific polyolefin. CONSTITUTION:The objective adhesive composition can be obtained by carrying out a graft copolymerization to (A) 100pts.wt. of a crystalline polyolefin with a degree of crystallinity >=10% and an intrinsic viscosity (eta) of 0.5-5dl/g (pref. of a molecular weight distribution index Mw/Mn ranging from 1 to 10, e.g. polyethylene), of (B) 0.1-50 (pref. 0.2-20)pts.wt. of a styrene hydrocarbon (e.g. styrene). This composition will be applied to an aromatic polymer (e.g., consisting of polyethylene terephthalate). USE:For ordinary miscellaneous goods, interior automotive trims, construction materials, industrial materials, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention exhibits excellent adhesive performance when laminating aromatic polymers such as adhesives for aromatic polymers, particularly polyethylene terephthalate, polycarbonate, and polyphenylene oxide, and polyolefins. The present invention relates to an adhesive for aromatic polymers that can be used for aromatic polymers. Aromatic polymers such as polyethylene terephthalate, polycarbonate, and polyphenylene oxide are widely used in applications such as food containers, packaging materials, daily necessities, automobile interior materials, construction materials, and industrial materials. Among these uses are chemical resistance,
In applications that require performance such as water resistance, hot water resistance, and gas barrier properties, attempts have been made to laminate polyolefins such as polyethylene and polypropylene onto the aromatic polymer in order to impart these properties. However, an adhesive with excellent adhesive performance has not yet been developed. For example, even if epoxy group-containing polyolefin, which is known as ordinary adhesive polyolefin, is used as an adhesive when laminating polyolefin and aromatic polymer, excellent adhesive performance cannot be obtained, and aromatic polymer Even if it is attempted to directly laminate these modified polyolefins into a composite, the same excellent adhesive performance cannot be obtained.

The present inventors have developed an adhesive for aromatic polymers, particularly an adhesive for aromatic polymers that can exhibit excellent adhesive performance when laminating an aromatic polymer layer and a polyolefin layer. As a result of searching, it was discovered that the above object could be achieved by using a modified polyolefin with specific properties obtained by graft copolymerizing styrenic hydrocarbons as an adhesive, and the present invention was achieved.

To summarize the present invention, the present invention comprises adding 0.1 to 5 parts of styrenic hydrocarbon (b) to 100 parts by weight of crystalline polyolefin (a) having a degree of crystallinity of 10% or more.
A modified product graft copolymerized in a range of 0 parts by weight,
The gist of the present invention is an adhesive for aromatic polymers other than styrenic polymers, which is made of a styrenic hydrocarbon graft-modified polyolefin having an intrinsic viscosity [η] of 0.5 to 5d6/g.

The adhesive for aromatic polymers of the present invention is a modified polyolefin obtained by graft copolymerizing a styrene hydrocarbon onto a specific polyolefin. Base polyolefin (a) constituting the styrenic hydrocarbon graft modified polyolefin
The polyolefin needs to have a crystallinity of 10% or more, and is preferably a crystalline polyolefin having a crystallinity of 15% or more. Further, the base polyolefin (a) has an intrinsic viscosity [η] [1 in decalin solvent
Value measured at 35°C] is usually 0.5 to 5c! ,6
/gs is preferably in the range of 0.7 to 4a5/g, and its density is usually 0.80 to 0.98 g/Cm',
It is preferably in the range of 0.84 to 0.96. Moreover, the molecular weight distribution (W/n) of the base polyolefin (a)
is usually in the range of 1 to 20, preferably 1 to 10, and a narrower molecular weight distribution is particularly preferred because adhesive strength improves. The base polyolefin (a
), the performance of the adhesive made of the styrenic hydrocarbon graft copolymer-modified polyolefin decreases in adhesive strength because the mechanical strength of the adhesive decreases. The base polyolefin (a
) is a single polymer of α-olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, and 1-decene. It can refer to a copolymer or a copolymer of two or more mixed components. Further, the base polyolefin may contain a trace amount, for example, 0.5 mol % or less of a diene component, but a smaller amount is preferable.

The graft component (b) of the styrenic hydrocarbon graft copolymer-modified polyolefin constituting the adhesive for aromatic polymers of the present invention has the general formula [I] [wherein R1, R2 and R3 are each a leaf atom or a lower Indicates an alkyl group.

] This is a compound represented by Specifically, styrene,
α-methylstyrene, 0-methylstyrene, m-methylstyrene, p-methylstyrene, m-ethylstyrene,
p-ethylstyrene, 0-isopropylstyrene, m-
Examples include inpropylstyrene and p-inopropylstyrene. Among these styrenic hydrocarbon components, styrene, m-methylstyrene or p-
- A methylstyrene component is preferred.

The ratio of the styrene hydrocarbon component of the styrene hydrocarbon graft copolymerized modified polyolefin of the adhesive for aromatic polymers of the present invention is 71 to 10% of the base polyolefin.
It is necessary to range from 0.1 to 50 parts by weight, more preferably from 0.2 to 20 parts by weight. When the graft ratio of styrenic hydrocarbon becomes less than 0.1, the performance of the adhesive made of the styrenic hydrocarbon graft copolymerized polyolefin decreases in its compatibility with aromatic polymers. The adhesive strength with the combined layer decreases,
When the amount exceeds 50 parts by weight, the compatibility with the polyolefin decreases, resulting in a decrease in adhesive strength with the polyolefin layer. Furthermore, it is necessary that the monomer-based hydrocarbon graft copolymerized modified polyolefin has an intrinsic viscosity [η] of 0.5 to 5 dl/g and a crystallinity of 10% or more, and is the limiting viscosity [η
] is in the range of 0.7 to 466/g and the crystallinity is preferably in the range of 15% or more. Further, the density of the styrenic hydrocarbon graft copolymerized modified polyolefin is usually in the range of 0.83 to 0.9 s gA', preferably 0.84 to Q, and 96 g/Cm3,
Further, its molecular weight distribution (+aw7Mn) is usually in the range of 1 to 25, preferably 1 to 15, and that 23
Melt viscosity at 0°C is preferably 10 to 5×1
0 voice, particularly preferably in the range of 50 to 8 x 105 voice. The intrinsic viscosity [η] of the styrenic hydrocarbon graft copolymer-modified polyolefin is 5 de/g
If the size is larger, the melt viscosity of the adhesive made of the styrene-based hydrocarbon graft copolymer-modified polyolefin becomes very large, resulting in poor lamination formability.
If it is smaller than 67 g, the melt viscosity is too low and it becomes difficult to mold it with a normal extruder, and even if it is molded with force, the strength as an adhesive is insufficient, resulting in a decrease in adhesive strength. Further, when the crystallinity of the styrenic hydrocarbon graft copolymer-modified polyolefin becomes less than 10%, the adhesive strength of the adhesive made of the styrene hydrocarbon graft copolymer modified polyolefin decreases due to insufficient adhesive strength. I come to do it. 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. This is preferred because it improves adhesive performance. The proportion of the styrenic hydrocarbon homopolymer contained in the styrenic hydrocarbon graft copolymerized modified polyolefin is preferably 100 mol % with respect to the grafted styrenic hydrocarbon component unit contained in the graft copolymerized modified polyolefin. Below, the range is particularly preferably 50 mol% or less. The adhesive for styrenic polymers of the present invention may be composed only of the styrenic hydrocarbon graft copolymer-modified polyolefin, but other components may be added to form a composition within a range that does not impair adhesive performance. There's no harm in it.

The styrenic hydrocarbon graft copolymer-modified polyolefin, which is the adhesive for aromatic polymers of the present invention, can be produced by a conventionally known method. For example, the base polyolefin (a) and the styrenic hydrocarbon (
b) may be reacted in a heated molten state, or may be reacted in a solution state. The reaction may be carried out in the presence of a radical initiator, if necessary. As radical initiators, organic peroxides, organic bersesters such as benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxy)-1
2,5-dimethyl-2,5-di(peroxidebenzony))hexyne-3,1,4-bis(tert-butylberoxoisopropyl)benzene, lauroyl peroxide, tert-butylberacetate, 2,5-dimethyl -2,5-di(tert-butylperoxy)hexyne-3,2,5-dimethyl-2,5-di(tert
;-butylperoxy)hexane, tert-butylberbenzoate, tert-butylberbenzoate), tert-butylberisobutyrate, tert-butylberbenzoate, tert-butylberbenzoate;
-butyl beru-5ea-octoate, tert-butyl berpivalate, cumyl berpivalate and tert
There are t-butylbergiethyl acetate and other azo compounds such as azobisisobutyronitrile, dimethylazoisobutyrate. Among these, dicumyl peroxide, di-tθrt-butyl peroxide, 2,5-
Dimethyl-2,5-di(tert-butylperoxy)
Hexyne-3,2,5-dimethyl-2,5-di(ter
t-butylperoxy)hexane, 1,4-bis(ta
Dialkyl peroxides such as rt-butylperoxyisopropyl)benzene are preferred. The temperature during the reaction is usually 70 to 350°C, preferably 80 to 32°C.
It is in the range of 0°C.

The adhesive for aromatic polymers made of the styrene-based hydrocarbon graft copolymer-modified polyolefin of the present invention can also be used to bond aromatic polymers together; It is preferable to use it for adhesion. The adhesive may be used as either a melt-type adhesive or a solution-type adhesive. It is made of an aromatic polymer to which the adhesive of the present invention can be applied, and may be in any shape, including various shapes, sheets, films, etc. The aromatic polymer is an aromatic polymer other than a styrene polymer containing a styrenic hydrocarbon component unit. More specifically, bisphenol A
Aromatic polycarbonates such as polycarbonate of bisphenol F, polycarbonate of bisphenol AD, polyphenylene oxide such as polyphenylene oxide, modified polyphenylene oxide, grafted polyphenylene oxide, polyethylene terephthalate, polybutylene terephthalate, polyethylene terephthalate inphthalate 1 polyethylene Examples include aromatic polyesters such as 2,6-naphthalene dicarboxylate, 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, it is preferable to apply the adhesive of the present invention to polyethylene terephthalate, polycarbonate, and polyphenylene oxide. Further, as the polyolefins to which the styrenic polymer adhesive comprising the styrene hydrocarbon graft copolymer-modified polyolefin of the present invention is applied, the polyolefins exemplified as the base polyolefin may be similarly exemplified. I can do it.

Next, the present invention will be specifically explained using examples.

Example 1 Ethylene-propylene copolymer [ethylene content 80 mol%, intrinsic viscosity (77) 1-3 dl/g (Mw/M
n) 2.7, crystallinity 15%] Styrene graft modified ethylene/propylene copolymer obtained by graft copolymerizing 2 parts by weight of styrene to 100 parts by weight [[η) 1.4 de/g]
s crystallinity 14%, (Mw/M n) 2.9, melt viscosity 3X105 boids] was melted in one extruder and fed to a three-layer composite T-die sheet forming die at a resin temperature of 200 °C. . Separate speed high density polyethylene [η)) 1.5+J/
g and polycarbonate (manufactured by Yadaikasei Co., Ltd., trade name Panrai L-1250) were each melted in separate extruders, and supplied to the die at a resin temperature of 200°C% and 280°C, respectively, to form an outer layer. is a high-density polyethylene layer (50μ),
The middle layer is a styrene-grafted modified ethylene/propylene copolymer layer (20μ), and the inner layer is a polycarbonate layer (1m).
A three-layer sheet consisting of m) was prepared.

A test piece with a width of IQmm was cut out from this three-layer sheet, and the part between the polycarbonate and styrene graft modified ethylene/propylene copolymer was peeled off, and the two-layer film side of high density polyethylene and styrene graft modified ethylene/propylene copolymer was removed. The interlayer adhesive strength between the polycarbonate and the styrene-grafted modified ethylene/propylene copolymer was measured by peeling it off at 180 degrees.

As a result, the adhesive strength was 600 g/CrR. Furthermore, the bond between the high-density polyethylene and the styrene graft modified ethylene/propylene copolymer was not separable and 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 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 base ethylene polymer for modification.

Examples 14 to 16 A propylene polymer shown in Table 2 was used as the base polyolefin for modification, and a propylene/ethylene random copolymer [ethylene content 2 mol%, [η]2.5ie/g) is used.
A three-layer sheet was prepared in the same manner as in Example 1, and the adhesive strength between the polycarbonate and the modified propylene polymer on the styrene graph 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:) 3-Oa6/g] was used as a polyolefin that adhered to the styrene graft modified polybutene-1. )
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 18 The styrene graft-modified poly-4-methylpentene-1 shown in Table 2 was used as an adhesive with polycarbonate, and the styrene-graft-modified poly-4-methylpentene-1
4-methylpentene as a polyolefin that adheres to
1 (98 mol%)-decene-1 (2 mol/l/%) copolymer (Crr': J 2.5 de/g), the styrene-grafted poly4-methylpentene-1 and 4-
A three-layer sheet was prepared in the same manner as in Example 1, except that the temperature at which the methylpentene-dodecene-1 copolymer was supplied to the die was 260°C.

The adhesive strength is shown in Table 2.

Example 19 A p-methylstyrene graft modified ethylene/propylene copolymer (
p-methylstyrene content 1-5E/100g P E
% (17') 1.5 de/'gz A six-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 510 g.
/ff.

Examples 20 and 21 As the aromatic resin, grafted polyphenylene oxide (manufactured by Asahi Dow @, trade name: Zylon 300) and polyethylene terephthalate (manufactured by Kanebo Co., Ltd., EFG-6) were used instead of polycarbonate. A six-layer sheet was prepared in the same manner as in Example 1 except that the temperatures were 320°C and 270°C, respectively.

As a result, the delamination strength was 800 g/(7) and 7
Ivy at 50g/CIn.

Examples 22 and 23 The styrene-grafted modified ethylene-propylene copolymer used in Example 1 and the same ethylene-propylene copolymer used as the base for modification in Example 1 were mixed in ratios of 50150 and 10/90. The mixture was mixed using an extruder. A three-layer sheet was prepared using the obtained styrene-modified ethylene-propylene copolymer composition in the same manner as in Example 1, and the interlayer adhesive strength was measured.

As a result, the adhesive strength was 49,087 points and 195 g, respectively.
/4.

Applicant: Mitsui Petrochemical Industries, Ltd. Agent Kazu Yamaguchi

Claims (1)

[Claims] (1) Modified crystalline polyolefin (a) having a degree of crystallinity of 10% or more, graft copolymerized with 0.1 to 50 parts by weight of styrenic hydrocarbon (b) to 100 parts by weight a substance whose limiting viscosity [η] is 0
．． 5 to 5 J/g and crystallinity is 10%
An adhesive for aromatic polymers other than styrene thread polymers comprising a styrene hydrocarbon graft-modified polyolefin within the above range.