JPS6013828A - Olefinic polymer mixture - Google Patents

Abstract

PURPOSE:The titled mixture providing a molded article having improved coating performance and adhesiveness free from smell, obtained by blending an organic compound containing a peroxide bond and an OH group with an organic peroxide containing no OH group. CONSTITUTION:(A) 100pts. wt. olefinic polymer is blended with (B) 0.1-50pts.wt., especially 0.3-20pts.wt. compound shown by the formula I [R<1> and R<2> are H, or CH3; R<3> is 2-6C alkylene; Y and Z are H, 1-20C hydrocarbon residue, or OH group-containing organic residue containing a bond selected from ether, ketone, and ester in the molecule; W is phenyl, CN, etc.; X is component prepared by polymerization of a compound shown by the formula II (R<5> is H, or 1-4C alkyl; R<6> and R<8> are 1-4C alkyl; R<7> is 1-12C alkyl, etc.) or a compound shown by the formula III; l, m, n, and p are 1-10,000, and m is 0 or <=(l+m+n)Xp], and (C) 0.01-20pts.wt., especially 0.1-7pts.wt. organic peroxide containing no hydroxyl group.

Description

[Detailed description of the invention] [I] Purpose of the invention The present invention relates to olefinic polymer compositions.

More specifically, (A) olefin polymer, (B)
The general formula relates to an olefin yarn mixture consisting of an organic compound containing a peroxide bond and a hydroxyl group represented by the IJ formula and (C) an organic peroxide not containing a hydroxyl group, and has excellent paintability and adhesion. The purpose is to provide a mixture that not only has excellent properties but also has no odor.

BACKGROUND OF THE INVENTION As is well known, olefin resins not only have excellent moldability but also have good properties such as mechanical strength, heat resistance, solvent resistance, and chemical resistance, so they are widely manufactured industrially. It is used in many fields as a general-purpose resin. However, since olefin resins do not have polar groups in their molecules (so-called non-polar), they are chemically extremely inactive polymeric substances. Furthermore, it not only has high crystallinity but also extremely low solubility in solvents, so when used in fields such as painting and adhesion, it has very low paintability and adhesiveness.

As mentioned above, although olefin resins have excellent moldability and the above-mentioned properties, olefin resins are used in fields where good adhesiveness and paintability are required (e.g., automobile parts, home appliance parts). The use of resin naturally had its limitations.

In order to solve the problems of adhesion and paintability of olefin resins, various methods as described below have been proposed for quite some time.

(a) A method in which an olefin resin or a molded product thereof is surface-treated from the outside and modified by a physical or chemical method (hereinafter referred to as "modification method").

(b) A method of adding other polymeric substances or additives to the olefin resin.

Hereinafter, among these methods, the modification method will be explained in more detail and problems will be described.

This method includes ``flame treatment method, plasma treatment method, ozone treatment method, corona discharge treatment method, and irradiation treatment method using ultraviolet rays or electron beams'' [hereinafter referred to as ``denaturation method (a month'') and ``chromic acid treatment method''. A method of treatment using a mixed solution and a mineral acid such as concentrated sulfuric acid, and a chemical treatment such as grafting using a compound containing a polar group on the olefin resin or its molded product in the presence or absence of a crosslinking agent. method" [hereinafter referred to as "denaturation method (b)"].

These modification methods provide chemically active sites rich in polar groups to the surface of the olefin resin or its molded product, and also physically roughen the surface. As a result, it is thought that the effects of improved paintability and adhesiveness can be obtained.

However, in order to carry out this modification method (a), the shape of the molded object to be treated must be significantly limited, and furthermore, the treatment effect not only deteriorates significantly over time by leaving it after the treatment, but also The degree of activation is often not always sufficient. Moreover, it has disadvantages such as being economically disadvantageous because it requires various expensive processing equipment.

In addition, among the modification methods (b), the treatment method using mineral acids not only tends to cause the chemicals used to be a source of pollution, but also requires complicated post-treatment steps such as neutralization, water washing, and drying. be. Furthermore, chemical treatment methods such as grafting require a drying step, require careful consideration of monomer application, grafting atmosphere, etc., and require a relatively long grafting reaction time. Therefore, it has drawbacks such as not being suitable for continuous production.

As described above, although the modification methods can improve the paintability and adhesion to some extent, they cannot be said to be satisfactory improvement methods because each method has various drawbacks.

Furthermore, as a method for imparting paintability and adhesion to the surface of olefin-based polymer molded products, polyolefins are prepared by graft-polymerizing chlorinated polypropylene or maleic anhydride onto the surface of the molded product before applying paint or adhesive. A method has been developed to apply a primer whose main ingredients are:

However, the method of applying a primer increases the cost by adding one step of coating or adhesion.

Including the above, olefinic polymers, modified products and mixtures thereof that do not impair the above-mentioned properties and processability of olefinic polymers and have good adhesiveness and paintability have not yet been developed.

Based on these facts, the present inventors conducted various searches for producing olefin polymers and olefin polymer mixtures with excellent paintability and adhesive properties, and as a result, (A) 100 parts by weight of olefin polymer; (B)
Paintability of a molded product of a mixture consisting of 0.1 to 50 parts by weight of an organic compound having at least one unsaturated bond in the molecule and containing a hydroxyl group and 0.01 to 20 parts by weight of (C) an organic peroxide. discovered that the adhesion properties were extremely good, and proposed
No. 36502, No. 57-68608 and No. 57-6
No. 8609). However, in molded products of this mixture, organic compounds containing hydroxyl groups may remain unreacted in the resulting mixture, and since these organic compounds are generally low molecular weight, they cannot be molded. Odors can sometimes be a problem when manufacturing molded products, as well as when using and processing molded products.

ClID Structure of the Invention Based on the above, the present inventors have searched various ways to produce an olefin polymer that not only has excellent paintability but also has no odor in molded products. (A) Olefin polymer Polymer 100 parts by weight, (B)
01 to 50 parts by weight of an organic compound containing a peroxide bond and a hydroxyl group represented by formula (I) below (hereinafter referred to as "hydroxyl compound") and (C) an organic peroxide having no hydroxyl group 001
It has been discovered that an olefin polymer mixture consisting of ~20 parts by weight does not have the above-mentioned drawbacks, has excellent paintability and adhesion, and can provide odorless molded products, and the present invention has been made based on the present invention. Reached.

Effects of the existing invention If the mixture according to the present invention is used, the following effects will be exhibited.

(1) An excellent coating or adhesive can be obtained without carrying out the above-mentioned modification of the surface as conventionally done.

(2) Since a paint having an isocyanate group can be applied directly to the surface of a molded product without applying a primer in advance, a coated product with good oil resistance can be obtained.

(3) Similar to (2), various materials (for example, wood,
Can be easily bonded to various metals.

(4) A laminate with polyurethane foam can be created at the same time as foaming is carried out on the molded product using a method such as injection foaming.

(5) Since no odor is generated during the production of molded products or when the molded products are processed, there is no problem in terms of environmental hygiene, and the product can be used in a wide variety of fields.

The mixture obtained according to the present invention can be used in a wide variety of ways to achieve the above-mentioned effects.

Typical usage examples are shown below.

(1) Automotive parts such as bumpers, instrument panels, armrests, door liners, seat backs, duct covers, etc. (2) Home appliance parts such as the interior and exterior of coolers and refrigerators (3) Roof panels, insulation walls, bathroom doors, etc. Materials for housing (4) Daily necessities such as dining tables, desk surfaces, furniture panels, kitchen cabinets, ice boxes, etc., furniture (5) Freezer components such as interior materials for refrigerated trucks and freezer walls■ Detailed description of the invention (A) Olefin Olefinic polymers used in the present invention include ethylene homopolymers, propylene homopolymers, random or block copolymers of ethylene and propylene, and ethylene and/or propylene copolymers with a large number of carbon atoms. Examples include random or block copolymers with 7 other α-olefins (the copolymerization ratio of α-olefin is at most 20% by weight).The molecular weight of these olefin resins is generally 2 to 2. 1 million,
Those having a molecular weight of 20,000 to 500,000 are preferable, and olefin resins having a molecular weight of 50,000 to 300,000 are particularly suitable. Also, low density (0,900i
10n3) or high density (0,980g'/Cm3)
Preferred are ethylene homopolymers, propylene homopolymers, random or block copolymers of ethylene and propylene, and random or block copolymers of ethylene or propylene with other α-olefins.

These olefin polymers are obtained by using a catalyst system (so-called Ziegler catalyst) obtained from a transition metal compound and an organoaluminium compound, and by supporting a chromium compound (for example, chromium oxide) on a carrier (for example, silica). They are obtained by homopolymerization or copolymerization of olefins using catalyst systems (so-called Phillips catalysts) or radical initiators (for example organic peroxides).

Furthermore, the KH of the present invention also includes modified polyolefins obtained by graft polymerizing compounds having at least one double bond (for example, unsaturated carboxylic acids, vinyl silane compounds) to these olefin polymers.

The production methods for these olefin polymers and modified polyolefins are well known.

These olefin polymers and modified polyolefins may be used alone or in combination of two or more. Furthermore, two or more of these olefin polymers and modified polyolefins may be resin blended in any proportion and used.

(B) Hydroxyl Compound The hydroxyl compound used in the present invention is represented by the following formula [Formula (I)].

3H In formula (1), R and R2 may be the same or different and are a hydrogen atom or a methyl group, and R3 has 2 carbon atoms.
~6 alkylene groups, Y and 2 may be the same or different, and are hydrogen atoms or hydrocarbon residues or molecules with 1 to 20 carbon atoms selected from the group consisting of ethers, ketones, and esters It is an organic residue containing oxygen having at least one type of bond, and 0 is -Cl (however, R4 is a hydrogen atom or a group having 1 to 1 carbon atoms).
6 alkyl groups), X is a component produced when the compound represented by the following formula (1) or (2) is polymerized, (wherein, R is a hydrogen atom or a carbon number R'7 is an alkyl group having 1 to 4 carbon atoms, and R'7 is an alkyl group having 1 to 4 carbon atoms, and R6 and R'7 may be the same or different. (a cycloalkyl group having 3 to 12 carbon atoms) °1.Dou10H.

H3 1 is an integer from 1 to 10,000, m is O or 1 to
10. ．． 000, n is an integer from 1 to 10,000, and p is an integer from 1 to 10,000, but (
l! +m+'n) X'p is at most 10,000
It is. In addition, if n/l + m is less than 0.05, the effect of improving the paintability of the mixture is small, so it is less than 0.05.
The above is desirable. The compound represented by formula (1) is a compound having at least one copolymerizable double bond and a peroxide bond in the molecule (hereinafter referred to as a "copolymerizable peroxide compound") and a vinyl type monomer having a hydroxyl group. copolymerization with the copolymerizable peroxide compound under conditions such that the peroxide bonds of the copolymerizable peroxide compound are not cleaved.
Alternatively, a copolymerizable peroxide compound, a vinyl monomer having a hydroxyl group, and a vinyl monomer not having a hydroxyl group are combined under conditions such that the peroxide bonds of the copolymerizable peroxide compound are not cleaved. It can be obtained by copolymerizing with.

Copolymerizable peroxide compounds include tertiary-butyl peroxyallyl carbonate, tertiary-hexyl peroxyallyl carbonate, 1,1,3,3-tetramethylbutylperoxyallyl carbonate, p-mendamper Oxyallyl carbonate, tertiary-butylperoxymethallyl carbonate, tertiary-hexylperoxymethallyl carbonate, 1,1,3.3-tetramethylbutylperoxymethallyl carbonate, p-menthaperoxymethallyl carbonate carbonate, p-menthamperoxymethallyl carbonate, m-(E-class-butylperoxyisopropyl)isopyrobenylbenzene, and the like.

Furthermore, examples of the vinyl monomer having a hydroxyl group include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, and 2-hydroxypropyl methacrylate.

Furthermore, vinyl monomers that do not have hydroxyl groups are generally used as monomers or comonomers in the production of synthetic resins (polymers). Examples include styrene, acrylonitrile, acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, vinyl acetate, and vinyl chloride.

The bitroxyl compound of the present invention can be produced by a vinyl polymerization method using a polymerization initiator, that is, a bulk polymerization method, a solution polymerization method, or an aqueous solvent polymerization method (i.e., an emulsion polymerization method or a suspension polymerization method). can also be done. However, it is important to conduct the reaction under conditions that do not cleave the peroxide bonds of the copolymerizable peroxide compound.

For this purpose, a free radical polymerization initiator having a decomposition temperature lower than the decomposition temperature of the copolymerizable peroxide compound used is used to avoid cleaving the peroxide bonds of the copolymerizable peroxide compound, but to initiate free radical polymerization. The copolymerization agent must be copolymerized at relatively low temperatures to be effective.

Generally, the temperature is 110°C or lower, and preferably 10 to 90°C.

As a free radical polymerization initiator suitable for such a temperature range, one whose half-life is 1 minute at a temperature of 160° C. or lower is preferable. Representative examples of preferred free radical polymerization initiators include:
Acetyl cyclohexyl sulfonyl peroxide, inbutyl peroxide, diisopropyl peroxydicarbonate tertiary-butyl peroxydicarbonate/root, lauroyl peroxide, benzoyl peroxide,
Tertiary-butylperoxyisobutyrate, 1゜1-bis(tertiary-butylperoxyisobutyrate-1,1,1
-bis(tertiary-butylperoxy)3.3.5-1-limethylcyclohexane, perfXe salt azobisisoprodylonitrile, and the like.

A method for polymerizing vinyl monomers using these U copolymerizable peroxide compounds J is described in JP-A-52-1.
It is described in the publication specification of No. 53916.

(c) Organic peroxide Furthermore, the organic peroxide used in unexploded DA is a 41-organic peroxide that does not have a hydroxyl group, and is generally used as an initiator in radical polymerization and a crosslinking agent for polymers. It has a half-life of 100' per minute.
A temperature of 130° C. or higher is preferred, and a temperature of 130° C. or higher is particularly preferred. For the above temperature below 100℃,
Not only is it difficult to handle, but the effects of using it are not very noticeable, so it is not desirable. Representative examples of preferred organic peroxides include ketone peroxides such as 1,1-bis-tertiary-butylperoxy-3,3,5-trimethylcyclo5xane, dialkyl peroxides such as dicumyl tumeroxide, Hydroperoxides such as 2+5'7 methylhexane-2,5-hydroperoxide, diacyl peroxides such as benzoyl peroxide, and peroxyesters such as 2,5-dimethyl-2,5-dibenzoyl peroxyhexane are mentioned. It will be done.

(DJ Mixing ratio In producing the mixture of the present invention, the mixing ratio of the hydroxyl compound to 100 parts by weight of the olefin polymer is 0.1 to 50 parts by weight, preferably 0.2 to 30 parts by weight, particularly 0.3 to 20 parts by weight is suitable.1
0 (If the mixing ratio of the hydroxyl compound to 1 part by weight of the olefin polymer is less than 0.1 parts by weight, the effect of improving adhesion is insufficient. On the other hand, even if 50 parts by weight or more of the same product is used) However, the effect of improving adhesion depending on the amount used is not observed, and the original properties of the olefin polymer are impaired, which is not preferable.

Further, the mixing ratio of the organic peroxide to 100 parts by weight of the olefin polymer is 0.01 to 20 parts by weight, and 0.01 to 20 parts by weight.
．． 05 to 10 parts by weight is desirable, especially 01 to 7 parts by weight.
part is preferred. If the mixing ratio of the organic peroxide to 100 parts by weight of the olefin polymer is 0.01 parts by weight or less, not only the effect of improving adhesion is low, but also the durability of the adhesion strength of the mixture is reduced. On the other hand, if the amount exceeds 20 parts by weight, the excellent mechanical properties originally possessed by the polymer will deteriorate, which is undesirable in any case.

(B)? R. Production of compound and molded product To produce the mixture of the present invention, the olefin polymer, hydroxyl compound, and organic peroxide may be uniformly mixed within the above mixing ratio range. . In producing this composition, a part of the mixed components is mixed in advance to produce a so-called masterbatch, and this masterbatch and the remaining mixed components are prepared to form the mixture as described above. May be manufactured.

The mixture also contains a blade stabilizer, a metal deterioration inhibitor, a flame retardant, a coloring agent, an electrical property improver, a filler, and an antistatic agent, consisting of an olefin polymer, a hydroxy compound, and an organic peroxide. Additives such as lubricants, processability modifiers, and tack modifiers may be mixed as long as they do not impair the properties of the mixture of the present invention.

This mixture may be prepared by triblending using mixers commonly used in the olefinic polymer industry such as Henschel mixers, Banbury mixers, Niegoos, roll mills, and screw extruders. It can also be produced by melt-kneading using a mixer. At this time, a more uniform mixture can be obtained by triblending in advance and further melt-kneading the resulting mixture.

In the case of the second melt-kneading, if carried out at a high temperature, the olefin polymer may deteriorate.

However, the graft polymerization between the olefinic polymer and the hydroxyl compound must be carried out at a temperature at which the peroxide bonding portion of the hydroxyl compound and the organic peroxide decompose. From the above, this melt-kneading is generally carried out at a temperature of 160 to 300'C, although it varies depending on the type of hydroxyl compound and organic peroxide used.

Various molded articles may be produced from the composition thus produced by processing methods commonly used in the field of olefin polymers, such as extrusion molding, injection molding, and press molding. In this case, it is necessary to carry out the process at a temperature higher than the temperature at which the composition [grafted product] obtained as described above melts.However, if the process is carried out at a considerably high temperature, the olefin polymer may deteriorate. It goes without saying that the process must be carried out at a humidity that does not cause decomposition.

(F) Coating and bonding method The method of the present invention is achieved by uniformly coating the surface of the molded product obtained as described above with a coating material having an isocyanate group to a thickness of 1 to 500 microns (when dry). The purpose can be achieved.The application method is not a special method, and it is sufficient to apply the method generally used on the surface of metal or synthetic resin molded products.A typical method is to use a spray gun. Examples include a method of applying with a brush, a method of applying with a brush, and a method of applying with a roll coater.

According to the present invention, it is possible to obtain a molded article that not only has excellent adhesion and gloss on the coated surface, but also has excellent weather resistance and gasoline resistance, such as in the case of urethane coating, so it is possible to obtain a molded article that is used in automobile parts. It can be applied to etc.

Further, it is also suitable to utilize the applied coating film having isocyanate groups and further metallize it, or to stack different types of side slants.

Next, for bonding with an adhesive, an adhesive having an isocyanate group (for example, a solvent-based urethane adhesive, a water-based vinyl urethane adhesive) is applied to the surface of the obtained molded product, and the adhesive surface is coated with an adhesive having an isocyanate group. The adhesive body of the present invention can be obtained by bonding shapes of substances that can be bonded with an adhesive.

These substances include metals (e.g. aluminum, iron, copper, and their alloys), glass, paper, textiles, wood, leather,
Rubbers (e.g. nemeprenchone, urethane rubber 9,
phtadiene-based comb, natural comb], polar group-containing resins (eg, ABS resin, polyester, polyamide, polyacrylonitrile, and the above-mentioned olefin-based polymers). Shaped objects include thin objects (for example, foils, papers, films), sheet-like objects, board-like objects, plate-like objects, pipe-like objects, rod-like objects, container-like objects, spherical objects, and foil-like objects. , and others with complex shapes. Furthermore, it is not limited to two layers, and multiple layers are also possible.

Furthermore, in the case of polyurethane foam, the laminate of the present invention can be produced by simultaneously carrying out the formation reaction of the urethane polymer and the foaming on the surface of the molded product.

In manufacturing this laminate, no special equipment or special method is required. That is,
Foaming methods commonly used in the field of polyurethane foam manufacturing such as injection foaming, mold foaming, and spray foaming may be used. Furthermore, the polyols, isocyanate compounds, blowing agents, etc. used as raw materials for polyurethane foam do not need to be special materials, and any commonly used materials may be used without any limitation.

In addition, in performing the above-mentioned coating, adhesion, and lamination, in the conventional method, the surface of the molded article may be cleaned or degreased in the previous step. The main purpose of this is to remove surface stains caused by oils and fats, eliminate variations in adhesion, and further improve adhesion. Specific examples include a method of wiping off using an organic solvent such as isopropyl alcohol, toluene, or trichlene, or a method of immersing large molded products in such an organic solvent under heating or treating with heated steam. can give.

These degreasing and washing steps can be similarly applied to the molded product obtained by the present invention. Furthermore, the same effects as before can be expected without any influence.

4D Examples and Comparative Examples The present invention will now be explained in more detail with reference to Examples.

In addition, in the examples and comparative examples, the melt index (hereinafter referred to as "MJ") is JISK-67.
According to 60, the temperature is 190℃ and the load is 2.1
The measurement was carried out under the condition of 6 kg. Additionally, Melt Flow Index (hereinafter referred to as "MFIJ") is based on JIS K-6.
According to 758, the temperature is 230 °C and the load is 2.1
Measured under the conditions of 6K9.

In addition, for the paint film peel strength test, a strip specimen with a width of 10 rpm is cut out from the specimen, and after forcibly peeling off a portion of the paint film from one end of the specimen, it is used in a tensile test of glass stick, etc. The tensile speed was 50 using a tensile testing machine.
The paint film was peeled off for 7 minutes at a peel angle of 180 degrees and a temperature of 20 degrees Celsius, and the peel strength of the paint film at that time (1
/ / 10 wn). Furthermore, gasoline resistance is determined by making cross cuts on the coating surface at an angle of 30 degrees with an NT cutter, making cross cuts at room temperature (approximately 20 degrees or 30 degrees), and soaking in gasoline for 24 hours at room temperature (approximately 20 degrees Celsius). After immersing each test piece in the water, changes in the coating surface were observed.

In addition, for water resistance, a cross cut was made in the same way as the gasoline resistance test piece, and after each test piece was immersed in lukewarm water at 40°C for 240 hours, changes in the coating surface were observed. Furthermore, the adhesive strength was determined by cutting out the molded product of the olefin polymer mixture into 1 ocb strips, and adding 3 cm to the ends of the 1 ocb strips.
Adhesive was applied to the ×2crn area. A molded product of the olefin polymer composition obtained in the example or comparative example, a copper plate or a piece of wood is pasted to this adhesive part,
The sample was pulled at a tensile rate of 50/min, and the tensile shear stress at breakage was measured. Furthermore, the adhesion strength between the molded product and the polyurethane foam was determined by forming the polyurethane foam between flat test pieces arranged in parallel with an fj of 1 crn by an injection foaming method, and then using this sandwich-like test piece. A sample was cut to a size of 1 cm x 1 σ, and the upper and lower molded parts of the sample were held between the crosshead of a tensile tester and the tensile speed was set at 5 w in the direction perpendicular to the contact surface.
The sample was pulled under conditions of 7 minutes, and the strength when the sample broke was measured and defined as adhesion strength (K9./cm 2 ).

The physical properties and types of the olefin polymer, rubbery material, talc, hydroxyl thread, and organic peroxide compound used in the Examples and Comparative Examples are shown below.

[Propylene homopolymer]

As an olefin polymer, the density is 0.900.9/CT
Globylene homopolymer with n 3 and MFI of 4.0.9710 minutes [hereinafter referred to as JPP (1) J]
It was used.

[Block propylene copolymer]

In addition, as an olefin polymer, the content of ethylene is 1
2-〇 7”o with weight ratio, MFI of 2.0, 9/10 minutes, and density of 0.900 F/Cm3
Pyrene-ethylene block copolymer [hereinafter [PP(2)]
J) was used.

[Low density ethylene homopolymer]

Furthermore, as an olefin polymer, the density is 0917 g.
A low-density ethylene homopolymer (hereinafter referred to as "LDPEJ") having a particle size of 7 cm3 and M and I of 5.1 g/10 minutes was used.

[Hydroxyl compound]

As a hydroxyl compound, azobisisobutyroni)
A compound consisting of 2-hydroxyethyl methacrylate with a weight of 95 and tertiary-butyl peroxyallyl carbonate with a weight of 5, obtained by polymerization using IJ as a polymerization initiator [weight average molecular weight
Approximately 400,000 yen (hereinafter referred to as compound η), 30% 2-hydroxyethyl methacrylate, 65% styrene, and Compound consisting of 5 mN% tertiary-butyl peroxyallyl carbonate [Takuhoshi average molecular weight approximately 600,000,
Hereinafter, compound r (referred to as "B month") and 2- and droxyethyl methacrylate (hereinafter referred to as "compound (June)") were used.

[Ethylene-propylene t & rubber]

An ethylene-propylene copolymer rubber having an ethylene content of 72% by weight as a rubber-like material, a density of 0.869/Cl1t" and a density of 0.869/Cl1t". [hereinafter referred to as "EP RJ"] was used.

〔talc〕

Talc with an average particle size of 20 microns was used.

[Organic peroxide]

As an organic peroxide, benzoyl peroxide [[,
The following [referred to as poJ] was used.

Examples 1 to 8, Comparative Examples 1 to 3 The ingredients whose amounts are shown in Table 1 were mixed in advance for 10 minutes using a super mixer. Each of the obtained mixtures was passed through a vented extruder (diameter 5 Q mm).
Pellets were manufactured while kneading using a . Each of the resulting pellets was molded using a 5 oz injection molding machine.
A flat specimen (120X
15ow, thickness 2cm].

A two-component urethane paint (manufactured by Nippon P Chemical Co., Ltd., trade name R-257) was applied to one side of each specimen thus obtained using a spray gun to a thickness of 35 to 40 microns for a paint film peeling test. I sprayed it. Next, heat drying was performed at a temperature of 90° C. for 30 minutes. 1 at room temperature
After being left for a day and night, the coating film of each sample was tested for peel strength.

The results are shown in Table 2. Furthermore, each was tested for gasoline resistance and water resistance.

The results are shown in Table 2. In addition, in these tests, the state of change in the coating film is shown below.

○ No change at all, △ Partial peeling, × Complete peeling.

After cutting the above-mentioned flat specimen into 10 (771 x 2
0) and two-component curing water-based vinyl urethane adhesive (manufactured by Chuo Rika Kogyo Co., Ltd., trade name, Ricabond CR, -100
Samples of the resin parts used in each example or comparative example [hereinafter referred to as rAJ] copper plate thickness of 1 sq. After gluing together pieces of wood (lauan, 5 mm thick, hereinafter referred to as June) and leaving them at room temperature for 24 hours,
Adhesive strength was measured. The results are shown in Table 3.

Two test pieces obtained as described above were fixed in parallel with an interval of 1 crn, and polyurethane foam was produced between them by injection foaming.

The equipment for injection foaming and the raw solution for polyurethane foam are manufactured by Instaform Inc. (USA) under the trade name Insulvac#
#2o was used (expansion ratio: 40 times).

After being left for 24 hours after injection, the adhesion strength of each specimen to the polyurethane foam was measured. The results are shown in Table 3. In addition, in this test, if the adhesion strength is too strong and failure does not occur at the interface between the molded product part and the polyurethane foam part, and the polyurethane foam suffers cohesive failure, the "cohesive failure" column in Table 3 will be added. ”.

In all Examples and Comparative Examples 1 and 2, it was recognized that both during molding and in each of the molded products obtained, the odor was stronger than in the case of manufacturing molded products of ordinary olefin polymers. I couldn't. However, in Comparative Example 3, the odor of both the photomolded products obtained during molding was stronger than that of ordinary olefin polymers, and especially during molding, the odor was quite strong. Unfavorable in terms of environmental hygiene.

Comparative Example 4 PP (1) was injection molded in the same manner as above to produce a flat specimen. A thermosetting polypropylene primer (manufactured by Nippon P Chemical Co., Ltd., trade name RB-291, Glimmer Co., Ltd.) was applied in advance to one side of this sample to a film thickness of 13 to 1.
After spraying the film uniformly using a spray gun to a thickness of 5 microns, the film was dried by heating at a temperature of 90° C. for 30 minutes. Next, a two-component urethane paint was applied to the primer-coated surface in the same manner as described above, and heat-dried at a temperature of 9.0°C for 30 minutes. The peel strength of this coating is 1
It was 6oi/l:m. A water resistance test was conducted, but no change was observed in the paint film.

However, when a gasoline resistance test was conducted, the paint film completely peeled off. Also, apply a two-component room-temperature curing polyurethane adhesive (similar to the above) to this primer-coated surface.
(A) and (B) using bond KU-10).
Alternatively, it was laminated with the sample of (C) and left at room temperature for 24 hours, and then the adhesive strength was measured.

Adhesive strength is 2.5, Ky/cm2 in (A),
(B) 2.7 K9 patent applicant Showa Denko K.K. agent Patent attorney Sei Kikuchi

Claims (1)

[Claims] (A) 100 parts by weight of olefin polymer, (B)
An organic compound containing a peroxide bond and a hydroxyl group whose general formula is (11) 01-50 parts by weight 3H In the formula (1), R and R may be the same or different, and may be a hydrogen atom or a methyl group. Yes, R has 2 to 6 carbon atoms
Y and 2 may be the same or different, and are hydrogen atoms or hydrocarbon residues or molecules having 1 to 20 carbon atoms, and are from the group consisting of ethers, ketones, and esters. is an alkyl group of 1 to 6),
is a component produced when the compound represented by the following formula (1) or (2) is polymerized, and 7 (wherein, R5 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R6 and R8 may be the same or different and are an alkyl group having 1 to 4 carbon atoms, and R7 is an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group having 3 to 12 carbon atoms. ) CH2,, CH3 1 is an integer from 1 to 10.000, m is 0 or 1 to
is an integer of 10,000, n is an integer of 1 to 10,000, p is an integer of 1 to 10,000, but (V
'+m+n)X P is at most 10,000] and (C) an organic peroxide containing no hydroxyl groups 0.
An olefinic polymer mixture consisting of 0.1 to 20 parts by weight.