JPH0216788B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention provides adhesives for aromatic polymers, particularly polyethylene terephthalate, polycarbonate,
The present invention relates to an adhesive for aromatic polymers that can exhibit excellent adhesive performance when laminating aromatic polymers such as polyphenylene oxide and polyolefins. 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 applications, in applications that require performance such as chemical resistance, water resistance, hot water resistance, and gas barrier properties, polyethylene, polypropylene, etc. are added to the aromatic polymer to impart these properties. Attempts have been made to laminate polyolefins, but 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 a polyolefin and an aromatic polymer, excellent adhesive performance cannot be obtained; Even if one tries to directly laminate these modified polyolefins in 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 our research, we found that when a modified polyolefin with specific properties made by graft copolymerizing styrenic hydrocarbons is used as an adhesive,
The inventors have discovered that the above object can be achieved and have arrived at the present invention. To summarize the present invention, the present invention has a crystallinity of 10
Crystalline polyolefin (a) in the range of 100% or more
A modified product obtained by graft copolymerizing styrenic hydrocarbon (b) in a range of 0.1 to 50 parts by weight, and whose intrinsic viscosity [η] is 0.5 to 5.
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 a dl/g range. The adhesive for aromatic polymers of the present invention is a modified polyolefin obtained by graft copolymerizing a styrene hydrocarbon onto a specific polyolefin. The base polyolefin (a) constituting the styrenic hydrocarbon graft-modified polyolefin needs to have a crystallinity of 10% or more, and more preferably a crystalline polyolefin with a crystallinity of 15% or more. It is preferable. Moreover, the base polyolefin (a) is
Its intrinsic viscosity [η] [value measured at 135°C in decalin solvent] is usually in the range of 0.5 to 5 dl/g, preferably 0.7 to 4 dl/g, and its density is usually 0.83 to 0.98 g/cm ³ , Preferably it is in the range of 0.84 to 0.96. Further, 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)
When the crystallinity of the adhesive is less than 10%, the performance of the adhesive made of the styrene-based hydrocarbon graft copolymer-modified polyolefin decreases, as the mechanical strength of the adhesive decreases, resulting in a decrease in adhesive strength. The base polyolefin (a) is ethylene, propylene,
1-butene, 1-pentene, 1-hexene, 4-
A homopolymer of α-olefin such as methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene or a copolymer of two or more mixed components can be shown. Further, the base polyolefin may contain a trace amount of a diene component, for example, in a range of 0.5 mol % or less, but a smaller amount is preferable. The graft component (b) of the styrenic hydrocarbon graft copolymer-modified polyolefin constituting the aromatic polymer adhesive of the present invention has the general formula [] [In the formula, R ¹ , R ² and R ³ each represent a hydrogen atom or a lower alkyl group. ] This is a compound represented by Specifically, styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, m-ethylstyrene,
Examples include p-ethylstyrene, o-isopropylstyrene, m-isopropylstyrene, and p-isopropylstyrene. Among these styrenic hydrocarbon components, styrene,
A m-methylstyrene or p-methylstyrene component is preferred. The grafting ratio of the styrene hydrocarbon component of the styrene hydrocarbon graft copolymerized polyolefin of the adhesive for aromatic polymers of the present invention is 0.1 to 50 parts by weight based on 100 parts by weight of the base polyolefin.
It must be within the range of parts by weight, and
Preferably it is in the range of 0.2 to 20 parts by weight.
When the graft ratio of styrenic hydrocarbon is less than 0.1, the performance of the adhesive made of the styrenic hydrocarbon graft copolymerized polyolefin decreases in its compatibility with the aromatic polymer, and as a result, the aromatic polymer layer When the amount exceeds 50 parts by weight, the adhesion strength with the polyolefin layer decreases because the compatibility with the polyolefin decreases. Furthermore, the styrenic hydrocarbon graft copolymer-modified polyolefin must have an intrinsic viscosity [η] in the range of 0.5 to 5 dl/g and a crystallinity of 10% or more; η] is in the range of 0.7 to 4 dl/g and the crystallinity is preferably in the range of 15% or more. Further, the density of the styrenic hydrocarbon graft copolymerized polyolefin is usually 0.83 to 0.98 g/cm ³ , preferably
It is in the range of 0.84 to 0.96 g/ ^cm3 , and its molecular weight distribution (w/n) is usually 1 to 25,
Preferably in the range of 1 to 15, at 230℃
The melt viscosity at is preferably 10 to 5×10 ⁶
poise, particularly preferably in the range of 50 to 8×10 ⁵ poise. The intrinsic viscosity [η] of the styrenic hydrocarbon graft copolymer-modified polyolefin is 5.
When it is larger than 0.5 dl/g, the adhesive made of the styrenic hydrocarbon graft copolymer-modified polyolefin has a very high melt viscosity, resulting in poor lamination formability, and when it is smaller than 0.5 dl/g,
The melt viscosity is too low, making it difficult to mold using an ordinary extruder, and even if molded by force, the strength of the adhesive is insufficient, resulting in a decrease in adhesive strength. Furthermore, when the degree of crystallinity of the styrenic hydrocarbon graft copolymerized polyolefin becomes less than 10%, the adhesive strength of the adhesive made of the styrenic hydrocarbon graft copolymerized 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,
Particularly preferred is a range of 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, it is possible to employ 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 radical initiators, organic peroxides, organic peresters such as benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(peroxide benzoate) hexyne-3 ,1,4
-bis(tert-butylperoxoisopropyl)
Benzene, lauroyl peroxide, tert-butyl peracetate, 2,5-dimethyl-2,5-
di(tert-butylperoxy)hexyne-3,
2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, tert-butylperbenzoate, tert-butylperphenyl acetate,
tert-butyl perisobutyrate, tert-butyl per-sec-octoate, tert-butyl perpivalate, cumyl perpivalate and tert-butyl perdiethyl acetate, other azo compounds such as azobisisobutyronitrile, dimethyl azo There is isobutyrate. Among these, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(tert-
Dialkyl peroxides such as butylperoxy)hexane-3,2,5-dimethyl-2,5-di(tert-butylperoxy)hexane and 1,4-bis(tert-butylperoxyisopropyl)benzene are preferred. The temperature during the reaction is usually in the range of 70 to 350°C, preferably 80 to 320°C. The adhesive for aromatic polymers made of the styrene-based hydrocarbon graft copolymerized modified polyolefin of the present invention can also be used for adhesion between aromatic polymers; 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 polycarbonate,
Aromatic polycarbonates such as bisphenol F polycarbonate and bisphenol AD polycarbonate; polyphenylene oxides such as polyphenylene oxide, modified polyphenylene oxide, and grafted polyphenylene oxide; polyethylene terephthalate, polybutylene terephthalate, and polyethylene. Aromatic systems such as terephthalate/isophthalate, polyethylene/2,6-naphthalic acid dicarboxylate, polyphenylene terephthalate, bisphenol A/terephthalic acid copolycondensate, bisphenol A/terephthalic acid/isophthalic acid copolycondensate An example is polyester. 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 styrenic hydrocarbon graft copolymer-modified polyolefin of the present invention is applied, the polyolefins exemplified as the base polyolefin may be similarly exemplified. Can be done. Next, 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 (w/
Styrene graft modified ethylene/propylene copolymer obtained by graft copolymerizing 2 parts by weight of styrene to 100 parts by weight of Mn) 2.7, crystallinity 15% [[η] 1.4
dl/g, crystallinity 14%, (w/n) 2.9, melt viscosity 3×10 ⁵ poise] was melted in one extruder,
The resin was supplied to a die for forming a three-layer composite T-die sheet at a temperature of 200°C. Separate high-density polyethylene [η]
1.5dl/g and polycarbonate [Teijin Kasei Ltd.
manufactured by Panlite L-1250] were melted using separate extruders, and the resin temperature was set to 200℃ and 280℃, respectively.
The mixture was fed to the die to prepare a three-layer sheet consisting of an outer layer of high-density polyethylene (50 μm), an intermediate layer of styrene-grafted modified ethylene-propylene copolymer (20 μm), and an inner layer of polycarbonate layer (1 mm). A test piece with a width of 10 mm was cut from this three-layer sheet, and a portion of the polycarbonate and styrene graft modified ethylene/propylene copolymer was peeled off.
The two-layer film side of high-density polyethylene and styrene graft modified ethylene/propylene copolymer.
The interlayer adhesive strength between the polycarbonate and the styrene-grafted modified ethylene-propylene copolymer was measured by peeling at 180 degrees. As a result, the adhesive strength was 600 g/cm. Further, 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 3 were 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. A laminated sheet was produced and evaluated in the same manner. The results are shown in Table 1. Examples 10 to 13 Example 1 except that the ethylene polymer shown in Table 2 was used as the base ethylene polymer for modification.
A three-layer laminate sheet was produced in the same manner as in the above. The results are shown in Table 2.

【table】

【table】

[Table] 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]
A three-layer sheet was prepared in the same manner as in Example 1, except that 2.5 dl/g] was used, and the adhesive strength between the polycarbonate and the styrene graft-modified propylene polymer was measured. The results are shown in Table 2. Example 17 Using styrene graft modified polybutene-1 shown in Table 2 as an adhesive with polycarbonate,
And as a polyolefin that adheres to the styrene graft modified polybutene-1, polybutene-1
A three-layer sheet was prepared in the same manner as in Example 1, except that [[η]3.0 dl/g] was used, and its adhesive strength 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 was used as an adhesive with polycarbonate.
-4-methylpentene-1 (98 mol%)-decene-1 (2 mol%) copolymer [[η] 2.5 dl/g] as polyolefin that adheres to methylpentene-1
, and the supply temperature of the styrene-grafted poly4-methylpentene-1 and 4-methylpentene-1/decene-1 copolymer to the die was set at 260°C, respectively.
A three-layer sheet was produced in the same manner as in Example 1 except for the following. The adhesive strength is shown in Table 2. Example 19 As an adhesive layer that adheres to polycarbonate, p
- Methylstyrene graft modified ethylene/propylene copolymer (p-methylstyrene content 1.5g/
A three-layer sheet was prepared in the same manner as in Example 1, except that 100 g of PE, [η] 1.3 dl/g, and the base ethylene copolymer were the same as in Example 1). As a result, the adhesive strength with polycarbonate was
It was 510g/cm. Examples 20 and 21 Grafted polyphenylene oxide (Asahi Dow Co., Ltd.) was used instead of polycarbonate as the aromatic resin.
A three-layer sheet was prepared in the same manner as in Example 1, except that polyethylene terephthalate (manufactured by Kanebo Co., Ltd., trade name: Zylon 300V) and polyethylene terephthalate (EFG-6, manufactured by Kanebo Co., Ltd.) were used, and the resin temperatures were set at 320°C and 270°C, respectively. was created. As a result, the delamination strength was 800 g/cm and 750 g/cm, respectively.
g/cm. Examples 22 and 23 The styrene-grafted modified ethylene-propylene copolymer used in Example 1 and the ethylene-propylene copolymer also used as the modified base material in Example 1 were mixed in 50/50 and 10/90 ratios. They were mixed in an extruder in the following proportions. A three-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 strength was 490 g/cm and 195 g/cm, respectively.
g/cm.

Claims (1)

[Claims] 1. Graft copolymerization of styrenic hydrocarbon (b) in a range of 0.1 to 50 parts by weight to 100 parts by weight of a crystalline polyolefin (a) having a crystallinity of 10% or more. The intrinsic viscosity [η]
An adhesive for aromatic polymers other than styrenic polymers, comprising a styrenic hydrocarbon graft-modified polyolefin having a crystallinity of 0.5 to 5 dl/g and a crystallinity of 10% or more.