JPS585323A - Polyolefin composition - Google Patents

Abstract

PURPOSE:The titled composition excellent in adhesion and coatability, prepared by adding, to a polyolefin, a lactone addition polymer containing an ethylenically unsaturated double bond-containing organic acid and a lactone ring-containing compound as an essential component. CONSTITUTION:The purpose polyolefin composition is obtained from 100pts.wt. polyolefin (e.g., low-, medium- or high-density polyethylene) and 1-100pts.wt., pref., 2-20pts.wt. lactone addition polymer prepared by addition-polymerizing 1-50mol% ethylenically unsaturated double bond-containing organic acid (e.g., acrylic acid or maleic acid) and a lactone-ring-containing compound of the formula, wherein R1-2 are each H or an alkyl, cycloalkyl or alkoxy and n is 1- 5, e.g., beta-propiolactone. This composition has good adhesion to different resins such as nylon and can be suitably used in the production of multilayer moldings or multilayer films of such resins.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to polyolefin compositions with excellent paintability and adhesion.

In general, polyolefins have various properties such as excellent mechanical, optical, and chemical properties, low specific gravity, good moldability, and low price, so they are used in an extremely wide range of applications. .

However, since such polyolefin is a non-polar material, it has poor adhesive strength with resins such as nylon, polyester, or polycarbonate, and has poor paintability.
Adhesiveness to inorganic materials [4 is lacking, no reinforcing effect can be expected with reinforcing materials, and the strength decreases as more fillers are used, which is a major obstacle in practical use.

By the way, in order to eliminate these drawbacks, it is possible to graft an acid monomer such as acrylic acid or maleic anhydride to this polyolefin using a mixed reactor such as an extruder or a hot roll. Many methods of introducing groups have been proposed, but with these methods, it is extremely difficult to uniformly graft the acid monomer added in a short period of time and to increase the grafting rate. Therefore, problems such as odor caused by volatilization of the acid monomer, coloration and deterioration of physical properties due to decomposition of the base polymer itself, and equipment limitations of the kneading reactor remain unresolved, and the acid monomer content in the polyolefin does not increase significantly. From this, the paintability is still satisfactory,
The reality is that adhesive properties and reinforcing effects by reinforcing materials have not been achieved.

However, in view of the existence of various drawbacks as described above, the present inventors have developed a polyolefin composition that solves all of these drawbacks, namely adhesiveness, paintability, retention of reinforcing effect by reinforcing material, and a large amount of filler. The present inventors have now completed the present invention by discovering that no decrease in strength is observed even when used for □, and that a composition with extremely excellent properties such as improved impact resistance can be obtained.

That is, the present invention uses, as essential components, 100 parts by weight of a polyolefin, 1 to 50 mol% of an organic acid (b-1) having an ethylenically unsaturated double bond, and a compound having a lactone ring (b-2). The present invention provides a polyolefin composition comprising 1 to 100 parts by weight of a lactone addition polymer B) obtained by addition polymerizing 99 to 50 mol% of B).

Here, the above-mentioned polyolefin refers to a homopolymer or copolymer of olefin such as ethylene, propylene, butene or pentene,
Typical examples include low density, medium density and high density polyethylene, crystalline polypropylene or ethylene-propylene copolymers.

On the other hand, the organic acid (b-1) having an ethylenically unsaturated double bond is an ethylenically unsaturated dibasic acid, such as an unsaturated basic acid, an unsaturated dibasic acid, or an anhydride of a cough dibasic acid. It refers to a compound having a double bond and a carboxyl group or anhydrous carboxyl group. Among these, typical unsaturated basic acids include acrylic acid, methacrylic acid, crotonic acid, 2-pentenoic acid, and allyl. Acetic acid, hexenoic acid, offuranic acid, cyclopentenylic acid, cyclohexenylcarboxylic acid-p-vinylbenzoic acid,
Examples include cinnamic acid or 5-pyridyl acrylic acid,
Typical unsaturated dibasic acids include fumaric acid, maleic acid, chlormaleic acid, mesaconic acid, itaconic acid,
Bicyclo(2,2,i]hebutene-2,5-dicarboxylic acid or bicyclo(2,2,1)-5-methyl-5-heptene-2,3-dicarboxylic acid, etc. Typical basic acid anhydrides include maleic anhydride and itaconic anhydride.

In addition, the above-mentioned compound (b-2) having a lactone ring refers to books represented by the general formula, of which representative examples include β-propiolactone, α,α-dimethyl-β-
Propiolactone, α-methyl-β-propiolactone, r-butyrolactone, -valerocton, methyl-
δ-valerolactone, dimethyl-δ-valerolactone,
Ethyl-δ-valerolactone, methoxy-valerolactone, ethoxy-δ-valerolactone, C-caprolactone, methyl-I-caprolactone, dimethyl-monocaprolactone, ethyl-e-caprolactone, methoxy-ε-caprolactone, ethoxy- e-caprolactone, cyclohexyl-C-caprolactone, ω-enantholactone, methyl-ω-enantolactone, methoxy-ω-enantolactone, ethoxy-ω-enantolactone, and the like.

Thus, the lactone addition polymer B) used in the present invention is a compound (b-1') having an ethylenically unsaturated double bond and a lactone ring. b-2), but during the addition polymerization, stannous oftate,
stannic ophtate, potassium carbonate, magnesium carbonate,
Known and commonly used reaction catalysts or activators for lactone condensation such as sodium, potassium, sodium methoxide, zinc halate, conolate acetate, tetrabutyl titanate, dipropyl titanate, zinc oxide or triethylaluminum are used. , the concentration of these catalysts or activators depends on the supplied lactone ring-containing compound (b-2).
(1001 to 5% by weight, preferably α01 to Q
, 25% by weight is appropriate.

The addition polymerization to obtain the lactone addition polymer B) is also carried out at a temperature of 60 to 280°C, preferably 60 to 220°C.

Furthermore, if necessary, during the production or storage of the lactone addition polymer B), in order to prevent the polymerization of the ethylenically unsaturated double bonded gold-containing organic acid (b-1), hydroquinone, hydroquinone, etc. Known and commonly used polymerization inhibitors such as 7-methyl ether, p-benzoquinone or 1,4-naphthoquinone can also be used.

Further, the ratio of each of the above-mentioned organic acids (b-1) and compound (b-2) used in obtaining the lactone addition weight (dB) is 1 to 50 mol of the organic acid (b-1). %, preferably 6 to 50 mol% of the compound (b-
99-50 mol% of 2), preferably 94-50 mol%
This is the ratio.

The lactone addition polymerization (IB) thus obtained is 1 to 100 parts by weight per 100 parts by weight of the polyolefin,
It is preferably used in an amount of 2 to 20 parts by weight.

In addition to the above-mentioned polyolefin N and lactone addition polymer B), the composition tube of the present invention contains a radical generator, a crosslinking accelerator, a crosslinking aid, an antioxidant, and an ultraviolet absorber that are commonly used in polyolefins. It is possible to use additives, reinforcing materials, fillers, etc., among them, radical generators are used in the process of kneading the polyolefin and the lactone addition polymer (6). Carry out a graft reaction between both components 5
It is used for azo compounds such as azobisin butyronitrile, benzoyl peroxide, t-butyloxyperoxide, 1°6-bis(1-butylperoxy-1-propyl)benzene, dicumyl peroxide, etc. Oxide, 2,2-bis(t-butylperoxy)butane, 1,1-bis(t-butylperoxy)-5,5
-)limethylcyclohexene, 2.5-cy)thyl-2,
5-di(t-butylperoxy)hexane or 2,5
A typical example is a peroxide such as -dimethyl-2,5-di(t-butylperoxy)hexyne-3.

The amount of the radical generator used is α01 to 6 parts by weight, preferably α1 to 21 parts by weight, based on 100 parts by weight of the polyolefin (4).

Typical crosslinking aids include triallyl cyanurate, diallylphthalate, divinylbenzene, butadiene rubber, or unsaturated polyester, and typical crosslinking accelerators include triethertetramine, hexamethylenetetramine, and hexamethylenediamine. Polyamines and their derivatives such as carbamates; or ammonium benzoate, sodium stearate, potassium stearate, zinc oxide, magnesium oxide or zinc dioxide.

Further, in order to adjust the progress of crosslinking, it is also possible to add an antioxidant such as an amine type, phenol type, sulfide type, phenyalkane type or phosphine type, or to use various ultraviolet absorbers.

Furthermore, typical reinforcing materials include glass fiber, asbestos fiber, carbon fiber, rock wool, mica, or walrusdonite, and typical fillers include calcium carbonate, Merck, clay, aluminum hydroxide, and sulfuric acid. Examples include calcium, magnesium carbonate, silicic anhydride, calcium, titanium oxide, and water powder.

As described above, the composition of the present invention can be obtained by mixing the above-mentioned polyolefins and lactone addition polymerization (IB), or, if necessary, further adding the various additive components described above. A mixing roll, a Banbury mixer, a kneader or an extruder can be used to effect such cross-mixing. Also,
The temperature and time for such crosstalk vary depending on the capacity of the crosstalk device used, but it is approximately 100 to 50%
A temperature of 50° C. and a time of 0.5 to 30 minutes is suitable.

The polyolefin composition of the present invention has the following operational advantages and compositional features.

In other words, in conventionally known compositions using acid monomers such as acrylic acid and maleic anhydride, when kneaded in an extruder, the odor of the acid monomer in the compound may be noticeable, or depending on the type of acid monomer, the odor of the acid monomer may be noticeable. The monomer is violently scattered or sublimated, and it is not well kneaded into the cylinder, and there is a phenomenon of separation and retention of imma near the feeder. The mixed material retains the odor of the acid monomer and does not provide the expected properties, necessitating the use of a special kneading machine.

On the other hand, when using the composition of the present invention, not only does the compound itself have no bad odor, but also sufficient cross-mixing is possible using a general extruder, etc., and grafting progresses sufficiently, so that after cross-mixing, You can obtain a product that has no bad odor at all.

Furthermore, the composition of the present invention has good adhesion to other resins such as nylon, polycarbonate, or polyester, and is suitable for application to multilayer molded products and multilayer films with these resins. Furthermore, the composition of the present invention not only improves paintability but also improves impact resistance.

Next, the present invention will be specifically explained using Examples, Comparative Examples, and Application Examples. Hereinafter, all parts and percentages are based on weight unless otherwise specified.

Example 1 433 parts of methacrylic acid, 567 parts of ε-caprolactone,
0.05 part of tetrabutyl titanate and 43 parts of p-benzoquinone α were charged, the temperature was raised to 130°C, and the mixture was reacted for 6 hours to obtain a white solid 8-caprolactone addition polymer. Hereinafter, this will be abbreviated as polymer (B-1).

Thereafter, 10 parts of this polymer (B-1'), 1000 parts of polypropylene having a melt flow index (M, F, 1.) of 5, and 1 part of dicumyl peroxide were blended to form a polyolefin composition. I got something.

Thereafter, this blend will be kneaded in a reactor, which will be described as an application example.

Example 2 Melt index (M,
1. )-1, except that high-density polyethylene was used.
A polyolefin composition was obtained in the same manner as in Example 1.

Example 3 826 parts e-caprolactone, 174 parts acrylic acid, 108 parts stannous oftate and 0.1 p-benzoquinone
A white solid ε-caprolactone addition polymer was obtained in the same manner as in Example 1, except that 74 parts were used. Hereinafter, this will be abbreviated as polymer (B-2).

Hereinafter, this polymer (B-
A polyolefin composition was obtained in the same manner as in Example 1, except that 20 parts of Example 2) was used.

Example 4 In a reactor similar to Example 1, C-caprolactone 747
parts, 256 parts of maleic acid and tetrabutyl alpha titanate
074 parts were charged, the temperature was raised to 150°C, and the reaction was carried out for 6 hours to obtain a C11-caprolactone addition polymer.Hereinafter, this will be abbreviated as polymer (B-5).

Thereafter, polymer (B-3) was used instead of polymer (B-2).
A polyolefin composition was obtained in the same manner as in Example 3 except that .

Example 5 δ-valerolactone 8061115, acrylic acid 194
A white solid δ-valerolactone addition polymer was obtained in the same manner as in Example 1, except that 0.08 parts of tetrabutyl titanate and 19 parts of p-benzoquinone α were used. Hereinafter, this will be abbreviated as polymer (B-4).

Thereafter, polymer (B-4) was used instead of polymer (B-1).
A polyolefin composition was obtained by pressing in the same manner as in Example 1 except that .

Application Examples 1 to 5 Each of the formulations obtained in Examples 1 to 5 was premixed in a Henschel mixer for about 2 minutes and then mixed at a barrel temperature of 15
50u adjusted to 0-170℃, die temperature 180℃
The mixture was kneaded at 50 rpm using a +p extruder to form pellets. The actual temperature of the contents of this extruder is approximately 200℃
Met.

During cross-wire work using the extruder, there was no odor from the acid monomer, the product entered the cylinder smoothly, and there was no bad odor from the feeder.

Next, various pellet-shaped modified polyolefin compositions obtained in this way, that is, grafted products of polyolefin particles and lactone addition polymerization (mB), were placed in a cylinder at a temperature of 20°C.
Injection molding was carried out under the conditions of 0° C. and an injection pressure of 900 kllA-, and the resulting molded product was subjected to a paint adhesion test and an impact strength test.

On the other hand, each of these pellet-shaped modified polyolefin compositions was sandwiched between two steel plates of 0 and 1 part thickness that had been degreased with trichloroethane, melted and bonded to a thickness of 1 nm using a hot press molding machine, and then rapidly cooled. At least the obtained sample was also tested for adhesion to a steel plate.

The results of each of these tests are summarized in Table 1K.

Application example 6 and comparative application examples 1 to 3 M, F, 1. −5 to 1000 parts of polypropylene,
20 parts of the polymer (B-2) obtained in Example 3, 10 parts of dicumyl peroxide, and 400 parts of calcium carbonate.
Application Example 6 was obtained by pre-kneading the parts and pelletizing them in the same manner as in Application Examples 1 to 5. However, even when the filler was blended in this way, there was no problem in either the mixing process or the pelletizing process. There were no problems at all stages.

Thereafter, various trials were conducted on this pellet-shaped modified polyolefin composition (grafted product) in the same manner as in Application Examples 1 to 5. The results are summarized in Table 1.

On the other hand, M-F, 1. Using only the polyolefin of = 5, it was kneaded and pelletized in the same manner as in Application Examples 1 to 5, and then molded. This was designated as Comparative Application Example 1.

Also, M, F, 1. = 5, 1000 of polypropylene
4 parts of acrylic acid and 10 parts of dicumyl peroxide were kneaded to form a pellet in the same manner as in Application Examples 1 to 5, which was then molded. This was designated as Comparative Application Example 2.

In this case, a bad odor due to acrylic acid was emitted during kneading.

Furthermore, M, F, 1. -5 polypropylene 10
00 parts and 400 parts of calcium carbonate were kneaded to form a pellet-like product in the same manner as in Application Examples 1 to 5, which was then molded. This was designated as Comparative Application Example 3.

Next, various tests were conducted on the unmodified polyolefin compositions obtained in Comparative Application Examples 1 to 3 in the same manner as in Application Examples 1 to 5. These results are summarized in the first
Shown in the table.

However, the various tests shown in Table 1 were conducted in the following manner.

A two-component acrylic urethane paint was spray-painted on the plate obtained by press-molding the pellets, dried at 80°C for 60 minutes, and then placed in a room at 23°C and 65% R, H.
After leaving it to stand for 4 hours, 100 1wm square gobbles were made on the painted surface using a razor blade, cellophane tape was applied over the dots, and then the tape was peeled off.

The percentage of the number of stitches remaining on the coated surface without being peeled off was expressed. In other words, ro/100J shows the worst paint adhesion when it is completely peeled off, and l-
100/100'' indicates complete adhesion and represents the best paint adhesion.

A sample with steel plates bonded using a heat press molding machine was heated to 23°C.
After leaving the sample in a room with 65% RH for 24 hours, the sample was cut into 25 fin width pieces to prepare test pieces.

Next, this test piece is subjected to 180° peeling at a speed of 200 n+/I+DI using an Instron type tensile tester to peel the steel plate from the polymer.

Claims (1)

[Claims] t (4) 100 parts by weight of polyolefin and (B) 1 of organic acid (b-1) having an ethylenically unsaturated double bond.
A polyolefin composition comprising, as an essential component, 5 to 100 parts by weight of a lactone addition polymer obtained by addition polymerizing ~50 mol% and 99 to 50 mol% of a compound (b-2) having a craton ring. thing. 2 The above organic acid having an ethylenically unsaturated double bond (b
2. The composition according to claim 1, wherein -1) is an unsaturated hydrochloric acid. (5) The above organic acid having an ethylenically unsaturated double bond (b
The composition according to claim 1, wherein -1) is an unsaturated dibasic acid. Organic acid having the above ethylenically unsaturated double bond (b
2. The composition according to claim 1, wherein -1) is an anhydride of an unsaturated dibasic acid. 1. The composition according to claim 1, wherein the compound (b-2) having a craton ring is represented by the general formula.