JPH02185580A - Method of adhesion - Google Patents

Abstract

PURPOSE:To conduct adhesion having an excellent resistance to thermal aging without pretreatment of an adherend surface when the adhered comprising a molded article of a propylene polymer compsn. is adhered with a two- component adhesive mainly comprising a chlorinated polypropylene by specifying the propylene polymer compsn. CONSTITUTION:A propylene polymer compsn. is prepd. by compounding a propylene homopolymer (A) practically insol. in xylene at 30 deg.C and with a melt index of 0.01-100g/10min and/or an ethylene-propylene copolymer (B) contg. 5wt.% or lower ethylene; an ethylene-propylene random copolymer (C) practically sol. in xylene at 30 deg.C and contg. 25-70wt.% ethylene; an ethylene-vinyl ester copolymer (D) contg. 5.0-50wt.% vinyl ester; and if necessary a filler (e.g. talc). In the compsn., the melt index of the total of A, B, and C, the ratio of C to the total of A, B and C, and the ratios of D, the vinyl ester and the filler to the total of A, B, C and D are each specified.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method of adhering a molded product of a propylene polymer composition to a two-component chlorinated polypropylene adhesive without using a primer.

In more detail, the adhesion (
The present invention relates to a method for adhering a chlorinated polypropylene two-component adhesive with good adhesion and a molded article made of a propylene polymer composition having excellent mechanical properties such as rigidity and impact resistance.

[Conventional technology]

As is well known, propylene polymers not only have excellent moldability, but also have good properties such as mechanical properties, heat resistance, solvent resistance, oil resistance, and chemical resistance, so they are widely manufactured industrially. It is used in many ways as parts of automobiles, electrical appliances, electronic equipment, etc., and as daily necessities. However, not only does it not have a polar group in its molecule (so-called non-polar), but its solubility in most organic solvents is extremely low, so it has very poor adhesion with various adhesives (adhesives). poor. For these reasons, there are various problems. Regarding these problems, we will explain door lining, which is a part of the interior of an automatic vehicle, as an example.

PVC leather is usually used for door lining, and this PVC leather is laminated with polypropylene foam, polyethylene foam, polyurethane foam, etc., or PVC leather cannot be used as is because of its low rigidity. In order to increase the rigidity of lining materials, molded products of acrylonitrile-butadiene-styrene terpolymer resin (ABS resin) and press-molded hardboard products as base materials, and polypropylene resins blended with fillers such as this powder. It is used by bonding it to a board using an adhesive.

However, in recent years, with the desire to reduce the weight and cost of automobiles, polypropylene resin (propylene-based polymer), which is inexpensive and has good moldability, has been used instead of ABS resin, hardboard, and wood flour-containing polypropylene resin. is starting to be used.

[Problem to be solved by the invention]

However, as mentioned above, propylene-based polymers do not have polar groups in their molecules, making them extremely chemically inert polymers. ) is either undercoated with a propylene-based polymer and a primer that can adhere to it, or subjected to pretreatment such as plasma treatment, corona discharge treatment, or ultraviolet irradiation treatment, and then an adhesive is applied and the PVC leather is bonded. It's reality. Therefore, the production process takes time and costs are high.

Similar problems arise when manufacturing other automotive interior materials, such as instrument panels, pillars, ceiling materials, armrests, and other linings, when propylene-based polymers are used and PVC leather is bonded. There is.

Based on these facts, some of the inventors of the present invention have developed an adhesive that does not have these drawbacks, that is, does not require pretreatment that requires complicated operations, and has good adhesion with a chloroprene-based two-component adhesive. Not only that, but it also has excellent moldability.
Moreover, as a result of various searches for propylene-based polymer compositions that have the same mechanical properties (e.g., impact resistance, rigidity) as propylene-based polymers, and also have excellent appearance of molded products, we found that propylene-based polymers A copolymer of ethylene and vinyl acetate, a graft polymer obtained by graft polymerizing a propylene-based polymer with an organic compound containing an unsaturated bond containing a hydroxyl group, and a filler, etc. are mixed into the mixture. The composition obtained by
No. 7, No. 62-203014, No. 02-201852
No. 62-231171). Therefore, the purpose of the present invention is to establish an adhesion method that can exhibit almost the same effect even with a two-component mixture type adhesive whose main component is chlorinated polypropylene, which could not be solved by these inventions. That is.

[Means to solve the problem]

According to the present invention, these problems are solved when bonding a molded article of a propylene polymer composition and a two-component adhesive containing chlorinated polypropylene as a main component. (A) is substantially insoluble in xylene at a temperature of 30°C, and has a melt index (measured under conditions 14 according to JIS K7210, hereinafter referred to as rM I (1) J) of 0.01 to 100 g/10 (B) substantially soluble in xylene at a temperature of 30°C; Ethylene-propylene random copolymer with a copolymerization ratio of ethylene of 25 to 70% by weight, and (C) a copolymer of ethylene and vinyl ester with a copolymerization ratio of vinyl ester of 5.0 to 50% by weight Alternatively, it is a composition consisting of these and (D) a filler, and the M I (1) of propylene homopolymer, propylene-ethylene copolymer, and ethylene-propylene random copolymer is 0.05 to 80 dollars.
'/10 minutes, and the composition ratio of the ethylene-propylene random copolymer in the total amount of these polymers is 5
．． 0 to 35% by weight, and the proportion of ethylene and The composition ratio of the copolymer with vinyl ester is 5.0 to 35
% by weight, and the monomer units derived from vinyl ester in these polymeric substances are 2.5 to IO weight%, and the composition ratio of the filler to 100 parts by weight of the total ffi of these polymeric substances is A method of adhesion characterized in that the amount is at most 40% by weight. The present invention will be specifically explained below.

(A) Propylene homopolymer and propylene ethylene copolymer The propylene homopolymer used in the present invention is obtained by homopolymerizing propylene.

In addition, the propylene-ethylene copolymer is at most 5.0% by weight (preferably 4.5% by weight or less) of propylene.
It is obtained by copolymerizing ethylene. These polymers are substantially insoluble in xylene at a temperature of 30°C (the soluble content is usually 10% by weight or less, preferably 5.0% by weight or less).

The M I (1) of propylene homopolymer and propylene-ethylene copolymer is 0. O1 to 100g/10 minutes, and 0. O1 to 80 g/10 min is preferable, and 0.1 to 70 g/10 min is particularly preferable. M.I.
When a propylene homopolymer or a propylene-ethylene copolymer having a (+) value of less than 0.01 g/In is used, crosstalk is not good. On the other hand, if the amount of these polymers exceeds 100 g/10 minutes, the resulting composition will have poor impact resistance.

(B) Ethylene-propylene random copolymer Furthermore, the copolymerization ratio of ethylene in the ethylene-propylene random copolymer used in the present invention is 25 to 70% by weight, preferably 25 to 65% by weight, particularly 30% by weight.
~65% by weight is preferred. The copolymerization ratio of ethylene is 2
When using 5% by weight of ethylene-propylene random copolymer, the impact resistance of the composition is unsatisfactory. On the other hand, ethylene propylene random copolymers in which the copolymerization ratio of ethylene exceeds 70% by weight are not only difficult to manufacture, but also have problems in terms of the rigidity and heat resistance of the composition.

Furthermore, M of the ethylene-propylene random copolymer
I (1) is usually 0.0 for the same reason as in the case of propylene homopolymer and propylene-ethylene copolymer.
01~50g/10min, 0.01~30g1LO
minutes, particularly preferably 0.05 to 20 g/10 minutes.

Furthermore, the ethylene-propylene random copolymer has 3
It is substantially soluble in xylene at a temperature of 0°C (the insoluble content is generally less than 10% by weight, preferably 5% by weight).
0% by weight or less).

These propylene homopolymers, propylene ethylene copolymers, and ethylene-propylene random copolymers may be produced by homopolymerization or copolymerization, respectively, and mixed in the composition ratios described below when producing the composition of the present invention. It is also common to prepare propylene homopolymer and/or propylene-ethylene copolymer beforehand and to combine ethylene and propylene in the same polymerizer or in separate polymerizers in the presence of these polymers and the catalyst system used to make the polymer. It may also be produced by so-called block copolymerization, which is copolymerization in a polymerization vessel.

In any of the above cases, M I (
1) is 0.05-80gZlo, 0.1-8
0g/10 minutes is desirable, especially 0.1-70g/+
o minutes is preferred. If M I (1) of the total amount of propylene homopolymer and/or propylene-ethylene copolymer and ethylene-propylene random copolymer is less than 0.05 g/10 minutes, kneading properties are not good. Furthermore, the moldability of the resulting composition is poor. On the other hand, 80g/
If the time exceeds 10 minutes, the mechanical properties of the composition, especially the impact resistance, will be poor.

In addition, the ethylene content in the total amount of these polymers is 2.0 to 25% by weight as a monomer unit, and 3.0 to 25% by weight.
25% by weight is preferred, particularly 5.0 to 25% by weight. If the ethylene content in the total amount of these polymers is less than 2.0% as a monomer unit, there is a problem in the impact resistance of the composition. On the other hand, if it exceeds 25% by weight, the rigidity and heat resistance will be insufficient.

Furthermore, the composition ratio of the ethylene-propylene random copolymer in the total amount of the propylene homopolymer and/or propylene-ethylene copolymer and ethylene-propylene random copolymer is 5.0 to 35% by weight, 5.0 to 30% by weight is desirable, especially 7.0%
~30% by weight is preferred. If the composition ratio of the ethylene-propylene random copolymer to the total amount of these polymers is less than 5.0% by weight, the resulting composition will have poor impact resistance. On the other hand, if it exceeds 35% by weight, problems arise in terms of the rigidity and heat resistance of the composition.

(C) Ethylene-vinyl ester copolymer further,
The copolymerization ratio of vinyl ester in the ethylene-vinyl ester copolymer used in the present invention is 5.0 to 5.
0% by weight, particularly preferably 5.0 to 40% by weight.

If an ethylene-vinyl ester copolymer having a vinyl ester copolymerization ratio of less than 5.0% by weight is used, the modification effect will not be satisfactory, which is not desirable. on the other hand,
If an ethylene-vinyl ester copolymer with a copolymerization ratio of vinyl ester exceeding 50% by weight is used, it is not preferable because not only the physical properties of the composition deteriorate but also delamination occurs. The melt index of the ethylene-vinyl ester copolymer [measured according to JIS K7210 under conditions 4, hereinafter referred to as rM l (2) J] is generally 0.1 to 200 g/10 min, and 0.1 to 200 g/10 min. 1-15
0 g/j 10 minutes is preferable, and 0.5 to 100 g/10 minutes is particularly preferable. If an ethylene-vinyl ester copolymer having M I (2) of less than 0.01 g/10 minutes is used, the kneading properties will be poor. On the other hand, if an ethylene-vinyl ester copolymer exceeding 200 g/IO is used, the mechanical strength of the composition will be poor.

The vinyl ester preferably has at most 20 carbon atoms (preferably 4 to 16 carbon atoms). Suitable vinyl esters include vinyl acetate, vinyl propionate,
Vinyl butyrate, vinyl pivalate, etc.
In particular, vinyl acetate is most suitable.

Although the propylene polymer composition of the present invention can be produced by mixing the above propylene homopolymer and/or propylene-ethylene copolymer, the rigidity of the composition ( flexural modulus) can be improved. At this time, by blending the modified propylene polymer described later, -
layers can exhibit this effect. Also, ethylene-
By blending the propylene rubber and the ethylene polymer described below, the impact resistance of the composition can be improved.

(D) Filler The filler used in the present invention is generally one widely used in the fields of synthetic resins and rubber. Among these fillers, inorganic compounds that do not react with oxygen and water and do not decompose during kneading and molding are preferably used as inorganic fillers. Examples of the inorganic filler include oxides and hydrates (hydroxides) of metals such as aluminum, copper, iron, lead, nickel, magnesium, calcium, barium, zinc, zirconium, molybdenum, silicon, antimony, and titanium. It is broadly classified into compounds such as sulfates, carbonates, silicates, their double salts, and mixtures thereof. Representative examples of the inorganic filler are described in Japanese Patent Application No. 59-8585. Among these inorganic fillers, those in powder form have a diameter of 3011nm.
The following (suitably 1011 m or less) is preferable. Further, in the case of a fibrous material, it is desirable that the diameter is 1 to 500 I1 m (preferably 1 to 300 um) and the length is 0.1 to 6 mm (preferably 0.1 to 5 mm). Furthermore, it is preferable that the diameter of the flat plate is 30 um or less (preferably 10 um or less). Among these inorganic fillers, those in the form of flat plates (flake) and those in the form of powder are particularly suitable. Suitable inorganic fillers include talc, mica, silica, glass fiber, graphite, and the like.

Examples of organic fillers include wood flour, organic fibers, straw, rice husks, and peanut shells.

The wood flour is usually of 12 mesh pass, and preferably has an average particle size of 45 mesh pass or less. Note that the type of wood from which this wood powder is made is not particularly limited.

Organic fibers include animal fibers such as wool, cotton, jute,
These include plant fibers such as bulbs, and commonly used synthetic fibers such as vinylon fibers, polyester fibers, nylon fibers, and acrylic fibers.

Since the length and average diameter of the organic fibers vary depending on the use of the final polypropylene composition, mixing conditions, etc., they cannot be generally defined, but generally the average diameter is in the range of 3 to 500. Warehouse, average length 0.1-6m
m is appropriate.

In addition, straw is used after being cut to have the same average diameter and length as organic fibers from the viewpoint of mixability.

In addition, rice husks and peanut husks are crushed and used like the wood flour mentioned above.

(E) Modified propylene polymer This modified propylene polymer is a propylene polymer with
α, β-unsaturated carboxylic acid and/or its anhydride”
(hereinafter referred to as "carboxylic acid compound") and an organic peroxide.

(1) Propylene polymer The propylene polymer used to produce the modified propylene polymer includes propylene homopolymer,
Examples include block copolymers of ethylene and propylene, and block copolymers of propylene and other α-olefins having at most 12 carbon atoms (copolymerization ratio of α-olefins is at most 20% by weight). . The M I (+) of this propylene polymer is usually 0.01-100 g/1 from the viewpoint of moldability and mechanical properties of the resulting composition.
0 minutes, preferably 0, old to 50 g/10 minutes, particularly preferably 0.02 to 50 g/10 minutes.

(2) Carboxylic acid compounds The carboxylic acid compounds used to produce the modified propylene polymer of the present invention are α,β-unsaturated carboxylic acids and their anhydrides. The number of carbon atoms in the unsaturated carboxylic acid compound is usually at most 30, and preferably 25 or less.

The unsaturated carboxylic acid compounds are broadly classified into monobasic unsaturated carboxylic acids, dibasic unsaturated carboxylic acids, and anhydrides thereof. - Representative examples of basic unsaturated carboxylic acids include acrylic acid and methacrylic acid. Typical examples of dibasic unsaturated carboxylic acids include maleic acid, fumaric acid, itaconic acid, citraconic acid and
．． 6-endomethylene-1,2,3,6-titrahydrosis-phthalic acid is mentioned. Further, the anhydride is an anhydride of the dibasic unsaturated carboxylic acid, and includes maleic anhydride, citraconic anhydride, citraconic anhydride and 3.6-
Examples include endomethylene-1,2,3,6-titrahydrosis-phthalic anhydride.

(3) Organic peroxide Furthermore, organic peroxides are generally used as initiators in radical polymerization and crosslinking agents for polymers, and those with a half-life of 1 minute of 100°C or more are preferable.
Particularly preferred is a temperature of 130°C or higher. If the above-mentioned temperature is 100° C. or lower, it is not only difficult to handle, but also the effect of using it is not very noticeable, which is not desirable.

(4) Usage ratio In producing the modified olefin polymer, 100
The ratio of the carboxylic acid compound to the weight part of the propylene polymer is 0.01 to 10 parts by weight, and 0.02 parts by weight.
-10 parts by weight is preferred, particularly 0.02-7.0 parts by weight. If the ratio of the carboxylic acid compound to 100 parts by weight of the propylene polymer is less than 0.01 parts by weight, the effect of improving rigidity is insufficient. On the other hand, even if more than 10 parts by weight is used, no effect of improving rigidity is observed depending on the amount used.

Further, the mixing ratio of organic peroxide to 100 parts by weight of propylene polymer is 0.01-10 parts by weight,
0.01 to 7.0 parts by weight is desirable, especially 0.02 parts by weight.
~5.0 parts by weight is preferred. The mixing ratio of organic peroxide to 100 parts by weight of propylene polymer is 0.01
If the amount is less than 1 part by weight, not only the modification effect is low, but also the effect of improving the stiffness of the mixture is insufficient.

On the other hand, if it exceeds 10 parts by weight, it is undesirable in any case because the excellent mechanical properties of the polymer will be reduced.

(5) Method for producing modified propylene polymer In order to produce the modified propylene polymer of the present invention, the above propylene polymer, carboxylic acid compound and organic peroxide are treated (heated) at the above mixing ratio. ) can be manufactured by At this time, the propylene polymer, carboxylic acid compound, and organic peroxide may be mixed together during the treatment, but they must be mixed in advance in a triblend, or at a relatively low temperature (where the carboxylic acid compound does not react). temperature) and heating the resulting mixture as described below.

If the treatment is carried out at high temperatures, the propylene-based polymer may deteriorate. However, the graft polymerization between the propylene polymer and the carboxylic acid compound must be carried out at a temperature at which the organic peroxide used is decomposed. Based on the above, this treatment generally has a 180 to 3
It is carried out at 00°C (preferably 200-280°C).

Representative examples of the organic peroxides, mixing methods, treatment methods, etc. are described in detail in the specification of JP-A-58-154732.

(F) Ethylene-propylene rubber Further, the ethylene-propylene rubber used in the present invention is mainly composed of ethylene-propylene copolymer rubber obtained by copolymerizing ethylene and propylene, and ethylene and propylene. , 4-pentagene, ■, 5
- Straight or branched diolefins containing two double bonds at the ends, such as hexadiene and 3,3-dimethyl-1,5-hexadiene, ■, 4-hexadiene and 6-methyl to 1,5 - monomers such as linear or branched diolefins containing only one double bond at the end, such as hebutadiene, or bicyclo(2,2,1) - cyclic diene hydrocarbons, such as heptene-2 and its derivatives. It is a multicomponent copolymer rubber obtained by copolymerizing a small amount (generally 10% by weight or less) of The weight ratio of ethylene monomer units to propylene monomer units in these copolymer rubbers and multicomponent copolymer rubbers is usually 30:
70 to 80:20 is preferred, especially 40:G.

A ratio of 75:25 to 75:25 is preferable. These ethylene-propylene rubbers are produced by copolymerization or multicomponent copolymerization of catalytic ethylene obtained from transition metal compounds and organic aluminum compounds, and propylene, or ethylene, propylene, and the above monomers.

Muny viscosity CM of the ethylene-propylene rubber of the present invention
L1+4 (100°C)] is 10 to 140, and 15 to
A number of 120 is desirable, and a number of 30 to 110 is particularly preferred. If an ethylene-propylene rubber with a Mooney viscosity of less than 10 is used, moldability will improve, but not only will the effect of improving impact resistance be low, but layer delamination may occur when gate-cutting the molded product. , may cause trouble. On the other hand, if it exceeds 140, not only will it be difficult to disperse during kneading, but even if a uniform composition is obtained, flow marks, weld lines, etc. will be highly visible on the surface of the molded product. Therefore, a formed product with a good appearance cannot be obtained.

(G) Ethylene polymer Density 1 of the ethylene polymer used in the present invention
40.900g/cJ or more, and 0.900 to 0.9
75g/clTl is preferable, especially 0.910~
0.970 g/cJ is preferred.

Examples of the ethylene polymer include ethylene homopolymers and random or block copolymers of ethylene and α-olefin. In general, α-olefins having 3 to 12 carbon atoms (preferably 3 to 8 carbon atoms) are preferred. Representative examples of the α-olefins include propylene, butene-1, hexene-1, octene-1 and octene-1.
-Methylpentene-1. The copolymerization ratio of α-olefin is generally at most 20% by weight, and preferably 10% by weight or less.

M l (2) of the ethylene polymer is at least 0.
1 g/10 minutes, preferably 0.1 to 50 g/10 minutes, particularly preferably 0.5 to 50 g/10 minutes. If M I (2) is [1.1 g/l (less than 1 minute), the dispersibility will be poor and it will be difficult to obtain a uniform composition, and even if a uniform composition is obtained, The improvement in adhesion is slight and the appearance of the formed product is poor.

(H) Composition ratio In the composition of the present invention, the composition ratio of the ethylene-propylene random copolymer to the total amount of the propylene homopolymer, the propylene-ethylene random copolymer, and the ethylene-propylene random copolymer is 5. .0-3
5% by weight, preferably 5.0 to 30% by weight, 7.
0 to 30% by weight is preferred. If the composition ratio of the ethylene-propylene random copolymer to the total amount of these polymers is less than 5.0% by weight, the resulting composition will have poor impact resistance. On the other hand, if it exceeds 35% by weight, the stiffness of the composition will be poor.

In addition, propylene homopolymer, propylene-
Ethylene copolymers, ethylene-propylene, especially 7
, 0 to 80% by weight is suitable. The composition ratio of ethylene-vinyl acetate copolymer in these polymer substances is 5.
．． If the amount is less than 0% by weight, the resulting composition will not have good adhesion to the adhesive (two-component mixed type chlorinated polypropylene). On the other hand, if it exceeds 35% by weight, the mechanical properties (especially rigidity) of the composition are poor.

If the proportion of monomer units derived from vinyl esters and units derived from unsaturated carboxylic acid esters in these polymeric substances is less than 2.5% by weight, the resulting composition will not have good adhesion. On the other hand, if it exceeds 10% by weight, the mechanical strength (especially rigidity) of the composition is poor.

Furthermore, the composition ratio of the filler to 100 parts by weight of the total amount of these polymeric substances is at most 40 parts by weight, and 0.
．． It is preferably 1 to 40 parts by weight, particularly preferably 1.0 to 35 parts by weight. If the composition ratio of the filler exceeds 40 parts by weight/-26 parts by weight per 100 parts by weight of the total amount of polymeric substances, not only will the moldability be poor, but also the adhesion will be poor, and the impact resistance will be poor. .

Further, when an ethylene polymer is blended, the composition ratio thereof is at most 20% by weight, and particularly desirably 18% by weight or less, based on the total amount of the polymer. The composition ratio of ethylene polymer in the total amount of polymer is 20% by weight
If it exceeds this amount, the adhesiveness of the resulting composition will decrease.

Furthermore, when compounding ethylene-propylene rubber,
Its composition ratio is at most 2 with respect to the total amount of the polymers.
It is preferably 0% by weight, particularly preferably 15% by weight or less. When the composition ratio of the ethylene-propylene rubber in the total amount of the polymer exceeds 20% by weight, the resulting composition has good impact resistance, but other mechanical strengths (for example,
Rigidity) is not good.

In addition, when using an ethylene polymer and ethylene-propylene rubber together, it is preferable that the amount is at most 30% by weight based on the total amount of the polymer.

In addition, the composition ratio of the modified propylene polymer is 10 to 100 parts by weight with respect to 100 parts by weight of the filler described below,
It is preferably 10 to 80 parts by weight, particularly preferably 15 to 75 parts by weight. If the ratio of the modified propylene polymer to 100 parts by weight is less than 10 parts by weight, the resulting composition will not have good rigidity. On the other hand, even if it is blended in an amount exceeding 100 parts by weight, no effect on improving stiffness is observed depending on the amount used.

(J) Production of composition To produce the composition of the present invention, the propylene polymer or, depending on the purpose of use, the filler, modified propylene polymer, ethylene-propylene copolymer, and ethylene polymer are added to the propylene polymer. should be mixed uniformly. At this time, as mentioned above, propylene qt autopolymer and/or
Alternatively, the propylene-ethylene copolymer and the ethylene-propylene random copolymer may be produced by so-called block copolymerization, or separately produced products may be mixed at this stage. In addition, if necessary, oxygen, which is commonly used in olefin polymers,
Stabilizers against light or heat, flame retardants, processability improvers,
Of course, additives such as lubricants, antistatic agents and pigments may be added.

The compositions may be obtained by tri-blending using mixers such as tumblers, ribbon blenders and Henschel mixers, or by using batch mixers (e.g. Banbury mixers) or continuous mixers ( For example, the mixture can be kneaded using an extruder (extruder), but it can also be continuously kneaded using a continuous mixer as described above. Further, by using these methods in combination (for example, triblending and then continuously kneading), more uniform mixing can be achieved.

(K) Molding method The composition obtained in this way is usually molded into pellets, and the desired molded product is formed by molding methods such as injection molding and extrusion molding that are commonly used in the respective fields of thermoplastic resins. Manufactured in

Even when melt-kneading is performed when producing the above composition,
Even when molding, the temperature is higher than the melting point of the polymer used, but at a temperature that does not cause thermal decomposition. For these reasons, the temperature is generally 180-280°C (preferably 200-280°C).
60°C).

(L) Adhesive The adhesive used in the present invention is a two-component mixture type mainly composed of chlorinated polypropylene, and is generally used by dissolving the chlorinated polypropylene and the isocyanate compound in an organic solvent. Ru. The chlorine content of the chlorinated polypropylene is usually 5.0 to 40% by weight (preferably 7.0 to 35% by weight). Furthermore, the starting material polypropylene is of inferior quality, and its molecular weight is generally from 500 to 200,000 (preferably from 1,000 to 100,000). Additionally, organic solvents include aromatic hydrocarbons (e.g. toluene, xylene), ketones (e.g. methyl ethyl ketone), aliphatic or alicyclic hydrocarbons (e.g. hexene, cyclohexene).
and chlorinated hydrocarbons (eg, trichlorethylene, tetrachloroethylene, chlorocyclohexane).

Further, the content of nonvolatile substances dissolved in the organic solvent is usually 15 to 30% by weight. The organic solvent may be used alone,
Alternatively, a mixed solution may be used. For handling reasons, the viscosity of the solution containing the adhesive is usually 100-2.0 at 23°C.
00 centipoise.

(M) Adhesive method To apply adhesive to the surface of the molded product obtained as described above, generally 100 to 200 g/rr is applied. (As a solvent containing adhesive, the same applies below). As for the application method, it is sufficient to apply a method generally used in industry. Typical methods include air spray method, roll coating method, dip coating method, and brush coating method. A robot may also be used. After coating, the organic solvent may be almost completely evaporated. At this time, if the film dries rapidly, bubbles may form in the film or the film may not be formed uniformly.

Therefore, initially at a relatively low temperature (e.g. 50-90℃)
to dry, then increase the temperature (130-150℃)
This allows crosslinking, adhesion and drying to be carried out simultaneously. Alternatively, after the surfaces of the adherends are bonded together, they may be crimped using a press under low pressure.

[For production]

It is thought that this will be effective.

[Examples and comparative examples]

Hereinafter, the present invention will be explained in more detail with reference to Examples.

In addition, in the examples and comparative examples, the flexural modulus is AS
Measurements were made according to TM 0790 and Izod impact strength was measured according to ASTM D256.

In addition, room temperature adhesion was measured using a deck test case made by injection molding (thickness 31111@s 140 x 140
mm, textured product) and chlorinated polypropylene two-component mixed type solvent-based adhesive (degree of chlorination obtained by chlorinating non-grade polypropylene with an average molecular weight of approximately 8,600, approximately 29% by weight) An organic mixture of the same volume of toluene and methyl ethyl ketone containing about 27% by weight of non-volatile components such as chlorinated polypropylene and isocyanate compounds) was sprayed at 100 to 150 g/rf.
After applying it evenly so that )
mutually bonded to the propylene resin foam surface,
Using a heating press machine (flat plate test one side at 50℃, PVC
The sheet side was subjected to a pressure of 1 kg/cd (150° C.) for 30 seconds. Next, it was placed in a constant temperature room (temperature 23℃, relative humidity 65%).
) for 48 hours. The resulting test piece was cut into 25 mm widths, the PVC sheet was forcibly peeled off from the resin part of the test piece, and the remaining adhesion part was tested using a tensile tester for 25 mm width.
against the PVC sheet at a speed of 0 mm/min (18
It was determined by tensile strength at 0 degrees) and measuring the peel strength. Furthermore, heat-resistant adhesion was determined by leaving the test piece obtained by pressure bonding as described above in a constant temperature room adjusted to 80°C for 300 hours, and pulling it at a temperature of 80°C in the same manner as above.
It was determined by measuring peel strength.

The physical properties of the propylene polymer, ethylene copolymer, ethylene-propylene rubber, ethylene polymer, modified propylene polymer, and filler used in Examples and Comparative Examples are shown below.

[(A) Propylene polymer]

As a propylene-based polymer, only propylene was polymerized in a polymerization vessel using a Ziegler-Natsuta catalyst without using a solvent. Then, ethylene was supplied to this polymerization vessel to produce a random copolymer of ethylene and propylene.

The obtained propylene polymer is a propylene homopolymer (
A composition with an ethylene-propylene random copolymer (soluble in xylene at a temperature of 30°C) containing 82% by weight of ethylene-propylene (insoluble in xylene at a temperature of 30°C) and having a copolymerization ratio of ethylene of 45% by weight. Met.

The M I (1) of this propylene polymer [hereinafter referred to as r P P (A) J] was 10 g/10 minutes. In addition, in the same way as this P P (A), only propylene was polymerized, and then ethylene and propylene were randomly copolymerized to form a propylene-based polymer [hereinafter r P P (
B) J) was produced. This P P (B) is an ethylene-propylene random copolymer containing 75% by weight of propylene homopolymer (insoluble in xylene at a temperature of 30°C) and a copolymerization ratio of ethylene of 50% by weight <3o°C. The composition was soluble in xylene at a temperature of M I (1) of this P P (B) is 8
．． It was 0g/10 minutes. For comparison, a composition containing 87% propylene homopolymer (insoluble in xylene) and an ethylene propylene random copolymer with an ethylene copolymerization ratio of 40% [composition M I ( 1)
15 g / 10 minutes, hereinafter referred to as r P P (C)J], Ml (1) Propylene homopolymer with a ratio of Og/Io minutes [hereinafter referred to as r P P (D) J: l, Ml
An ethylene-propylene random copolymer (hereinafter referred to as r PP (E) J) in which (1) was 12 g/10 minutes and the copolymerization ratio of ethylene was 2.0% by weight was used.

[(B) Ethylene copolymer]

In addition, as an ethylene copolymer, M I (2) is 3
0 g/10 min, and the copolymerization ratio of vinyl acetate is 3
3% by weight of ethylene-vinyl acetate copolymer [r
EVA (a) J), M I (2) is 21g/
Ethylene-vinyl acetate copolymer [hereinafter referred to as rEVA] in which the copolymerization ratio of vinyl acetate is 20% by weight
(b) J) and M I (2) are 7.2 g/1
Ethylene-vinyl acetate copolymer [hereinafter referred to as r E V
A (c) J), M I (2) is 45 g/L
Ethylene-methacrylate copolymer having an O content and a copolymerization ratio of methyl methacrylate of 35% by weight [
Hereinafter referred to as “EMMAJ” and M I (2) are 20
g/10 minutes and an ethylene-ethyl acrylate copolymer (hereinafter referred to as rEEAJ) having a copolymerization ratio of ethyl acrylate of 20% by weight was used.

[(C) Filler] Further, as a filler, talc having an average particle size of 2.0 mm and an aspect ratio of 5.5, and talc having an average particle size of 7.0 mm is used as a filler.
Mica, wood flour (45 mesh pass) and jute (average radius 2
0, average fiber length 3 mm) was used.

[(D) Modified propylene polymer]

In addition, as a modified propylene polymer, M 1 (1)
is (1,6 [/l (1 minute propylene homopolymer 100
0.70 parts by weight of maleic anhydride and 0.4 parts by weight
Parts by weight of benzoyl peroxide were previously triblended for 5 minutes using a Henschel mixer. The obtained mixture was kneaded using an extruder (diameter 40, cylinder temperature 180-230°C) to produce pellets (hereinafter referred to as "modified PPJ"), which were used.

[(E) Ethylene polymer]

Furthermore, M I (2) is 1. 0g/10 min and a density of 0.950 g/c++l [hereinafter referred to as rPE(1)J] and M I (2
) is 7.1g/10min and the density is 0.920g
Linear copolymer of ethylene and butene-1 which is /cnl [JjH polymerization ratio of butene-1 8.2% by weight, hereinafter r
P E (2) J] was used.

[(F) Ethylene-propylene rubber] Also, as the ethylene-propylene rubber, Mooney viscosity [MLl+4
(100°C)] is 60 and the copolymerization ratio of propylene is 27% by weight [hereinafter referred to as rEPRJ] and Mooney viscosity CML
1+4<100°C)) is 36, the copolymerization ratio of propylene is 36, and the copolymerization ratio of ethylidene norbornene is 6.0% by weight.
Propylene-ethylidene norbornene terpolymer rubber [
Hereinafter referred to as rEPDMJ] was used.

Examples 1 to II, Comparative Examples 1 to 8 A propylene polymer, an ethylene copolymer, and a filler whose amounts and types are shown in Table 1 were mixed for 5 minutes using a super mixer. Each of the obtained mixtures was passed through a vented twin-screw extruder (cylinder temperature: 180
Pellets (composition) were produced while kneading at ~200°C and a diameter of 30 m. Each pellet was used in a 5-ounce injection molding machine to produce flat plates, specimens for measuring flexural modulus, and specimens for measuring Izod impact strength. Izod impact strength of each specimen obtained (measurement temperature 23°C)
The flexural modulus and room temperature adhesion and heat resistant adhesion were also measured. The results are shown in Table 2.

In the columns of "Room Temperature Adhesion" and "Heat Resistant Adhesion" in Table 2, "material destruction" means that the foam of the propylene resin was destroyed.

(Leaving space below) (Part 1) Table (Part 2) Examples 12 to 19 Table 3 shows the amounts of P P (A) and modified propylene polymers, and Table 3 shows the types and types of each. Tri-blending was performed in the same manner as in Example 1 using the ethylene copolymer, ethylene polymer [hereinafter referred to as rPEI], ethylene-propylene rubber [hereinafter referred to as ``rubber''], and filler whose blending amounts are indicated. . The resulting mixture was kneaded in the same manner as in Example 1 to produce a pellet (composition). Using an injection molding machine in the same manner as in Example 1, each pellet was manufactured into a flat plate, a specimen for measuring a bending elastic modulus of 8Pj, and a specimen for measuring Izod impact strength.

The Izot impact strength and flexural modulus of each specimen obtained were measured, as well as the room temperature adhesion and heat-resistant pipe welding properties. The results are shown in Table 4.

(The following is a blank space) Table 1 [Effects of the Invention] The adhesive method of the present invention and the propylene polymer composition used in the adhesive method exhibit the following effects (characteristics).

Procedural amendment (voluntary)

Claims (1)

[Claims] When adhering a molded article of a propylene polymer composition to a two-component adhesive containing chlorinated polypropylene as a main component, the propylene polymer composition (A) 30 substantially insoluble in xylene at temperatures of
(B) substantially soluble in xylene at a temperature of 30° C.; and the copolymerization ratio of ethylene is 25 to 70% by weight
an ethylene-propylene random copolymer, and a copolymer of ethylene and vinyl ester in which the copolymerization ratio of (C) vinyl ester is 5.0 to 50% by weight, or these and (D) a filler. The melt index of propylene homopolymer, propylene-ethylene copolymer and ethylene-propylene random copolymer is 0.05 to 8.
0 g/10 minutes, and the composition ratio of the ethylene-propylene random copolymer in the total amount of these polymers is 5.0 to 35% by weight, and the composition ratio of the ethylene-propylene random copolymer to the total amount of these polymers is 5.0 to 35% by weight. The composition ratio of the copolymer of ethylene and vinyl ester in the total amount of the polymer substance consisting of the ethylene-propylene random copolymer and the copolymer of ethylene and vinyl ester is 5.0 to 5.0.
35% by weight, and the monomer units derived from vinyl ester in these polymer substances are 2.5 to 10% by weight.
and the composition ratio of the filler to 100 parts by weight of the total amount of these polymeric substances is at most 40% by weight.