JPS59226040A - Material attached to molded article of mixture of olefinic polymer - Google Patents

Abstract

PURPOSE:To obtain a material attached to a molded article having high bond strength free from smell, by bonding a molded article of a mixture of an olefinic polymer and an organic compound containing a peroxide bond and a hydroxyl group to the material by the use of an isocyanate group-containing adhesive. CONSTITUTION:An isocyanate group-containing adhesive is applied to the surface of a molded article of a mixture consisting of 100pts.wt. olefinic polymer (preferably one having 50,000-300,000mol.wt.) and 0.1-50pts.wt., preferably 0.3- 20pts.wt. organic compound shown by the formula I [R<2> and R<2> are H, or methyl; R<3> is 2-6C alkyl; X and y are H, group shown by the formula II, -O-O-R<5> (R<4> and R<5> are 1-100C hydrocarbon group, or organic residue containing bond selected from ether, ketone, ester, and peroxide, and not H simultaneously); Z is phenyl, CN, group shown by the formula III, etc.; l is 0-10,000; m and n are 1-10,000; (l+m)Xn is <=10,000], and the molded article is attached to a material which can be bonded by the adhesive.

Description

DETAILED DESCRIPTION OF THE INVENTION [I] OBJECTS OF THE INVENTION The present invention relates to adhesives for molded articles of olefinic polymer mixtures. More specifically, the surface of a molded product of a mixture consisting of (A) a 7-rufin polymer and (B) an organic compound containing a peroxide bond and a hydroxyl group whose general formula is represented by the formula (I). This product relates to an adhesive of a molded olefin polymer mixture obtained by applying an adhesive having a group to 1 and bonding an article that can be bonded with the adhesive, and has high adhesive strength. Rather, the purpose is to provide an odorless adhesive between molded products of the olefin polymer or between the molded products and other articles (e.g., wood, paper, metal, polar plastic). .

[11] Background of the Invention As is well known, olefin resins (olefin polymers) not only have excellent moldability, but also have high mechanical strength and
Because it has good properties such as heat resistance, solvent resistance, and chemical resistance, it is widely manufactured industrially and used in many fields as a general-purpose resin. However, olefin resins do not have polar groups in their molecules (so-called non-polar).
Therefore, it is a polymeric substance that is extremely chemically inert. Furthermore, not only is the crystallinity high, but the solubility in solvents is also extremely low, so when adhesives are used to adhere olefin resins to each other, or to adhere olefin resins to other articles, the adhesion is extremely low. .

As mentioned above, although olefin resins have excellent moldability and the above-mentioned properties, they are used in fields where good adhesion is required (e.g. automobile parts, home appliance parts). There were naturally limitations on what I could do.

In order to resolve the adhesive properties of olefin resins, various methods have been proposed for quite some time, such as those described below.

(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 olefin resin.

Among these methods, the variable fl near-j method will be explained in more detail below, and its problems will be described.

This method includes ``flame treatment method, plasma treatment method, maison treatment method,''1'' electric discharge treatment method, ultraviolet rays, and 13
1 using an electron beam (irradiation treatment method [hereinafter referred to as 1.1 denaturation method (a)]) and [treatment using a mineral acid such as concentrated sulfuric acid] h method 713 and olefin-based tree 1ift and 1jl for its molded product.
i7 of the crosslinking agent using a compound that has three El groups
: (method of chemical treatment such as t-F or Graph 1 in the absence of t-F) [hereinafter referred to as ``denaturation method (b)'').

By these modification methods, chemically active molecules rich in polar groups are added to the surface of olefin resins or their molded products.
and the surface is physically roughened. the result,
It is thought that the effect of improving adhesiveness can be obtained.

However, in order to carry out this modification method (a), the shape of the molded object to be treated is significantly limited, and furthermore, not only is the treatment effect significantly reduced over time by leaving it after the treatment, but also the In many cases, the degree of oxidation is 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 process, and not only do detailed considerations such as the coating of the simple substance and the atmosphere of graphs 1 to 1, but also the reaction time is relatively long.

Therefore, it has drawbacks such as not being suitable for continuous production.

As mentioned above, it is possible to improve adhesion and culmness with the modification method, but since all methods have their own drawbacks, no satisfactory improvement method can be used to improve the old deformation method. "stomach.

Furthermore, as a method to increase the adhesion (=J, L) to the surface of a molded product made of olefinic polymer, chlorinated polypropylene or maleic anhydride is added to the surface of the molded product before applying the adhesive. A method of applying a primer containing polyolefin or the like as a main component has been developed.

However, in the method of applying a primer, the cost increases because the number of steps for applying or adhering increases by -1.

Including the above, a satisfactory method has not yet been developed that does not impair the above-mentioned properties and processability of olefin resins, and the resulting adhesive has strong adhesive strength. .

Based on the above, some of the present inventors have searched various ways to obtain adhesives that firmly adhere molded products of olefin-based resins (olefin-based polymers) or mixtures thereof, and have found that (A) Olefin-based 100 parts by weight of polymer (B)
An organic compound that has at least one unsaturated bond in one molecule and contains a hydroxyl group (hereinafter referred to as "hydro").
An adhesive containing an isocyanate group is applied to the surface of a molded product of a mixture consisting of 0.1 to 50 parts by weight of (C) 0.01 to 20 parts by weight of an organic peroxide. However, by adhering the olefin polymer mixture to other articles that can be bonded with the adhesive, it was discovered that the adhesive formed from the olefinic polymer mixture obtained was a strongly bonded adhesive, and as previously reported. (Japanese Patent Application No. 57768609). However, in molded products of this mixture, organic compounds containing hydroxyl groups may remain unreacted in the resulting mixture, and since this organic compound generally has a low molecular weight, Odors can sometimes be a problem during manufacturing, use, and processing of molded products.

[111] Structure of the Invention Based on the above, the present inventors have conducted various searches to produce an olefin polymer that not only has excellent adhesive properties but also has no odor in molded products. A> 100 parts by weight of i-refine polymer and ([3) 0.1 to 50 parts by weight of an organic compound containing a peroxide bond and a hydroxyl group (hereinafter referred to as "hydroxyl compound") represented by formula (1) below. An olefinic polymer mixture obtained by applying an adhesive having a 1-isocyanate group to the surface of a molded product of a mixture consisting of a heavy W part, and then adhering it to another article that can be bonded with the adhesive. The present invention was achieved by discovering that the adhesive of the molded product does not have the above-mentioned drawbacks, not only does it adhere firmly, but also that the resulting molded product has almost no odor.

[rV] Effects of the Invention The adhesive produced by the present invention exhibits the following effects (characteristics) including its manufacturing method.

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

(2) A good adhesive can be obtained without applying a primer to the surface of the molded product in advance.

(3) Since there is no need to modify the surface of the molded product, there is no need for equipment associated with modification, there is no complexity in the process, and there is no possibility of unstable adhesion.

(4) The adhesive force between the molded product of the olefin polymer mixture and the adhesive is due to the chemical reaction between the hydroxyl compound grafted to the olefin polymer and the isocyanate group in the adhesive, so it has good solvent resistance. The secondary physical properties such as

(5) It also has excellent adhesive strength.

(6) Since no odor is emitted during the production of the molded product or when the molded product is used or processed, there is no problem in terms of environmental hygiene and it can be used in a wide range of applications.

The adhesive obtained by the present invention, including its manufacturing method, exhibits the effects (features) described above, so it can be used in a wide variety of fields.

Typical uses are shown below (2) Walls of refrigerators, exterior walls of refrigerators, panels, building panels, interior and exterior materials for doors, (2)
Tools, surfaces such as desks, furniture panels, kitchen 1117
Vinets 1~ (:I) Automobile instrument 1~Panel interior material (Δ) A Renoin polymer The olefin polymer used in the present invention, C is an ethylene homopolymer, a propylene homopolymer, polymer, 1
Random or block copolymers of brene and propylene, and random or block copolymers of ethylene and/or propylene with other α-A reflexes having at most 7 carbon atoms (the copolymerization ratio of α-olefins is high). 20% by weight). The molecule m of these olefin polymers is generally 2 to 100,000,
A resin having a molecular weight of 20,000 to 500,000 is preferable, and an A reflex resin having a molecular weight of 50,000 to 300,000 is particularly suitable. Also, low density (0,90h
/cm3) or high density (0,980o/ct3)
), 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 are preferred.

These olefin polymers are obtained by using a catalyst system (so-called Ziegler catalyst) obtained from a transition metal compound and an organoaluminum compound, and by supporting a chromium compound (for example, chromium oxide) on a support (for example, silica). Catalyst systems (so-called Phillips catalysts) or radical initiators (e.g. organic peroxides)
It can be obtained by homopolymerization or copolymerization of olefins using

Furthermore, in the present invention, compounds having at least one double bond in these olefin polymers (for example, unsaturated carboxylic acids, vinyl silane compounds) are shown in graph 1.
Also included are modified polyolefins formed by polymerization.

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

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

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

■ 3 1-1 In formula (I), R1 and R2 may be the same or different and are a hydrogen atom or a methyl group, and R3 has 2 carbon atoms.
-6 alkyl groups, X and Y may be the same or different, and are hydrogen atoms or groups represented by the general formula (However, R4 and R5 may be the same or different and are carbonized carbon atoms with 1 to 100 carbon atoms) It is a hydrogen residue or an organic residue containing oxygen having at least one type of bond derived from the liver consisting of ethers, ketones, esters, and peroxides), but X and Y are hydrogen at the same time. Z is or -C (R6 is a hydrogen atom or has 1 carbon number
~6 alkyl groups), the number is O or 1 to io,
ooo is an integer, m is an integer from 1 to io, ooo, and n is an integer from 1 to io, ooo, but (also -
t "Ron X n is at most to, ooo. Also,
When the ml value is less than 0.05, the effect of improving the adhesion of the mixture is small, so it is desirable that the ml value is 0.05 or more. [
i] The compound represented by the formula is generally produced by polymerizing a vinyl type monomer having a hydroxyl group or a vinyl type monomer having a hydroxyl group and a vinyl type monomer having a hydroxyl group using a polymeric peroxide as an initiator. (
can get.

The polymerization method is the same as that used for ordinary radical polymerization of vinyl monomers, and the bulk method, suspension polymerization method, and solution polymerization method L
13 and emulsion polymerization method, it can be easily polymerized by either method 1j.

As vinyl type monomers with human [1 xyl group, 2
-Human [J: 1xylmethacrylate, 2-human[Ixylmethacrylate-1, 2-hydroxypropyl acrylate-1, 2-human[1xypropylmethacrylate]
1~ etc. In addition, examples of vinyl monomers having no hydroxyl group include styrene, acrylonitrile
Lyle, acrylic acid, methacrylic acid, methyl acrylate,
Examples include ethyl chloride, ethyl methacrylate, ethyl methacrylate, vinyl acetate, and vinyl chloride.

Typical examples of polymeric peroxides used in the present invention include those whose chemical formula is represented by the following formula.

In formulas (1) to 10, X may be the same or different, and is 2 to 2o.

The manufacturing method and types of these hydroxyl compounds are described in JP-A TRI 53-149918@ &5 yo (J”
ml 55-75414, each publication number 11 Im.

(C) Mixing ratio The mixing ratio of the hydroxyl compound to 100 parts by weight of the olefin polymer for producing the mixture of the present invention is 0.1 to 50 parts by weight, and 0.2 to 30 parts by weight. Preferably, 0.3 to 20 parts by weight is particularly suitable. 1
If the mixing ratio of the hydroxyl compound to 00 parts 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 is used, the effect of improving adhesion depending on the amount used is not observed, and rather the inherent properties of the olefin polymer are impaired, which is not preferable.

(D> Production of mixture and molded product In order to produce the mixture of the present invention, the olefin polymer and the hydroxyl compound may be uniformly mixed so that the mixing ratio falls within the above range.

In producing this mixture, 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 mixed to produce the above-mentioned mixed components. Good too.

In addition, the mixture contains A-refin polymer J3 and human [1
Depending on the intended use of the mixture, these mixed components may also contain stabilizers against oxygen, heat and ultraviolet rays, metal deterioration inhibitors, flame inhibitors,
Colorants, electrical property improvers, fillers, antistatic agents, lubricants, processability improvers, J, and viscosity reduction↑! 1. i: Additives such as Q additives may be added within a range C that does 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, kneaders, roll mills, and screw extruders. It can also be produced by melting and mixing 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 above melt-kneading, if carried out at a high temperature, the olefin polymer may deteriorate. However, the graft polymerization between the olefin polymer and the hydroxyl compound must be carried out at a temperature at which the peroxide bonds of the hydroxyl compound are decomposed. From the above, this melt-kneading process is generally carried out at a temperature of 160 to 300°C, although it varies depending on the type of hydroxyl compound used.

The mixture thus produced is then added to methods commonly used in the field of olefin polymers, such as extrusion molding, injection molding, and press molding, to produce various molded products. That's fine.

At this time, it was obtained as described above.1. : It is necessary to conduct the process at a temperature higher than the temperature at which the mixture (Plano 1 to 1) becomes dissolved. () However, if the hot stone's cfi is quite high, the A-lenone-based polymerization may deteriorate, so do not carry out the decomposition below the temperature that will not cause it. There is C'.

([) Adhesion method L; ), and by adhering the shape of the bondable object 4c'i1 to the adhesive surface, the contact object of the present invention can be obtained. These substances include metals (for example, aluminum, iron, copper, and their alloys), glass, paper, fibers, wood, leather, rubbers (for example, neorene rubber, urethane rubber, butadiene rubber, natural rubber), polar group-containing resins (eg, ABS resin, polyester, polyamide, polyacrylonitrile, and the above-mentioned olefin polymers). In addition, as for shaped objects, natural 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,
Examples include boxed autumn items and other items with complex shapes.

Furthermore, it is not limited to two layers, and multiple layers are also possible.

[v1] Examples and Comparative Examples Hereinafter, the present invention will be explained in more detail through Examples 1!1
Do 1.

In addition, in Examples and Comparative Examples (, Mel I... index (hereinafter referred to as 1-M, 1.J) is JIS K-
According to 6760, the temperature is 190°C and the load is 2.
It was measured under the condition of +6k (]. Also, the melt flow index (r'MFIJ) was J 'I
Measurements were made in accordance with S K-'6758 at a temperature of 230° C. and a load of 2.16 Jl.

Furthermore, the adhesive strength was determined by cutting out a molded product of the olefin polymer mixture into a 10 cm x 2 cm triangular shape, and applying adhesive to the ends of the 30 m x 20 m area.

A molded product of the olefin polymer mixture obtained in the example or comparative example, a copper plate, or a piece of wood is glued to this adhesive part, and it is pulled at a tensile rate of 50 III/B), and the tensile strength at breakage is U. Measure the shear stress.

The physical properties and types of the olefin polymer, rubber, talc, and hydroxyl compound used in Actual hFA Example J5 and Comparative Example a3 are shown below.

[Propylene homopolymer J is an olefin polymer with a C density of 0.900 flll
/cm3c and an MFI of 4,0(]/10 minutes (hereinafter referred to as 1-1) P (1
) I used the name J.

"Zo I" Tsukub 1 pyrene copolymer] In addition, as an olefin polymer, C ethylene copolymer
il lfi 12.0 wt % C ant, and MFI
2. Oa/10 min C available, density 0.900g 7
cm3 propylene-ethylene 10x copolymer F
I used r P P (referred to as 21) below.

[Low density ethylene homopolymer] Furthermore, as an olefin polymer, the density is 0.917 (
+ 7cm3 with Te, Katsu V1.1. 5. fQ 7
Low density ethylene homopolymer which is 10 minutes rLDP
EJ) was used.

[Ethylene-propylene copolymer rubber] As a rubber-like material, the ethylene content is 72% by weight, the MFI is 0.8710 minutes, and the density is 0.8.
6 g/cm3 of ethylene-propylene copolymer rubber [
Hereinafter referred to as rEPRJ] was used.

[talc] The average particle size is 2.0 microns. I used talc.

L Hydroxyl Compound J As a hydroxyl compound, 98 parts by weight of 2-hydroxyethyl methacrylate and 2 parts by weight of a polymeric peroxide having the chemical formula "(n is approximately 5) were subjected to a normal suspension polymerization method at 70°C. - (The compound obtained by polymerization is the following one compound (Δ
) j, average weight of about 220,000], 2-human L] xy1 delmethacrylate] ~ 30 parts by weight, styrene 68 weight ω
Part J3 and 2 parts by weight of the above-mentioned polymeric peroxide are subjected to 1o-cr polymerization by a conventional suspension polymerization method to obtain 1 or less compound (B).
U, average molecule ■ Approximately 280,000 J J3 and 2-hydroxy J
Delmethacrylate 1 or higher (referred to as Fr compound (C)) was used.

1 (peroxide, Ijfil peroxide, dicumylper A4' lead 11X lower 1-1) CP J was used.

Examples 1 to E3, Comparative Examples 1 and 2 'Table 1' = (2 flii Hyakushu is expressed using iF>Rakkashime Super Mijuri - respectively)
) mixed for 1=. 1. Extrude each mixture into 1-1 extrusions iA<diameter! (l m m ) was used (kneaded) to produce 4 knots of 1 knot.

Each of the fT pellets was injection molded at a temperature of 230°C using a 5-ounce O'J injection molding machine.
Flat test plate (120 x 150 mm, thickness 2 mm)
, hereinafter referred to as "sample j of the resin part" was prepared.

After cutting this flat specimen into a 100m x 2cm square shape, a two-component room temperature curing solvent type polyurethane adhesive (manufactured by Konishi Co., Ltd., trade name, Bond KU-1) was used.
0) and two-component curing water-based vinyl urethane adhesive (manufactured by Chuo Rika Kogyo Co., Ltd., trade name Ricabond CR-100)
A sample piece of the resin part used in each example or comparative example was cut into a wedge shape of the same size [hereinafter referred to as r
(A) J], copper plate [thickness in+m, hereinafter referred to as r(B
) J] or wood (lauan wood, thickness 511111
1, hereinafter referred to as r<C)J] were glued together and left open for 24 hours at room temperature, and then the adhesive strength was measured. The results are shown in Table 2. In all Examples J and Comparative Example 1 and J3, all of the molded products obtained during molding were of ordinary olefin polymer molded products. It was not observed that the odor was stronger than in the case of manufacturing. However, comparative example 2
Both the odor during molding and the molded product obtained were normal A? Compared to the case of A-based polymers, the odor is strong, especially during molding, and therefore the ring-jMtQi-based polymer is not preferable.

(Blank below) Comparative Example 3 P P (1) was index-molded in the same manner as described above to produce a flat test piece. One side of this sample was coated with a thermosetting polypropylene primer (Nippon B Chemical Co., Ltd. product,
Product name RB-291, modified primer) with a film thickness of 13~
After spraying it uniformly using a spray gun to a thickness of 15 microns, it was heated and dried at 90° C. for 30 minutes. Next, a two-component room-temperature curing polyurethane adhesive (Bond KU-10) was applied to the brimer-applied surface in the same manner as described above, and the specimens of (A), (B), or (C) and the beams were bonded together. In addition, the adhesive strength was measured after being left at room temperature for 24 hours. Adhesive strength is 2 in (A)
．． 5kO/cm2, 2.8kg/cm2 in (B)
and (C) 2.2 kO/C1112 tea ivy.

Patent applicant: Showa Denko Co., Ltd. Agent: Patent Attorney Sei Kikuchi - 33/14) 0 shots clearer Minoru Takaishi 498-22 Yanoguchi, Inagi City

Claims (1)

Scope of Claims: (A) 100 parts by weight of an olefin polymer and (B) 0.1 to 50 parts by weight of a hexagonal compound containing a peroxide bond and a hydroxyl group whose general formula is represented by formula (I)
Weight part 3 11 In the formula (1), R1 and R2 may be the same or different, and have a hydrogen atom or a methyl group C, R3 is an alkyl group having 2 to 6 carbon atoms, and X and Y are the same or different. may be a hydrogen atom acid or a group having the general formula is an oxygen-containing organic residue having at least one type of bond selected from the group consisting of 1 atom or carbon number
~6 alkyl groups), l is 0 or 1-10,
000, rTl is an integer from 1 to 10,000, and n is an integer from 1 to 10,000, but (
l+m) Adhesive material for moldings of coalesced mixtures.