JPS5941374A - Adhesive for insert in pvc product - Google Patents

Abstract

PURPOSE:To obtain titled adhesive with high bonding potential of PVC products to aluminum- or iron-made inserts, by dissolving in an organic solvent each specific acrylic urethane and acrylic halogenated polymer, rubber curing agent (and promotor), and epoxy resin. CONSTITUTION:The objective adhesive can be obtained by dissolving in an organic solvent the following ingredients: (A) 100pts.wt. of an acrylic urethane prepared by the coplymerization between (i) 100pts.wt. of an urethane synthesized by the reaction between (a) a polyesterdiol with hydroxyl groups at both ends and (b) a diisocyanate in a unolar ratio NCO/OH of 1/0.6-5/0.95 and (ii) 50- 150pts.wt. of an least one sort of compound among (meth)acrylonitrile and (meth)acrylic acid (esters and their derivatives), (B) 2-50pts.wt. of an acrylic halogenated polymer prepared by the copolymerization between (iii) 100pts.wt. of a halogenated polymer and (iv) 10-50pts.wt. of the component (ii), (C) 5- 300pts.wt. of a rubber curing agent, (D) 5-300pts.wt. of a rubber curing accelerator, and (E) 10-300pts.wt. of an epoxy resin.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an adhesive for molding inserts, and more specifically, polyvinyl chloride (hereinafter referred to as PVC),
Concerning adhesives with strong adhesion to aluminum and iron inserts.

In this explanation, "part" refers to 1 part by weight.Synthetic resin side moldings attached to the body of automobiles and other vehicles are often directly affected by the outside temperature, and during the summer and winter, as well as during the day and night. Expands and contracts repeatedly due to large temperature changes.

As a result, the molding itself is curved, and the molding is likely to separate from the vehicle body due to the difference in expansion and contraction between the sheet metal part of the vehicle body and the molding itself.

For this reason, modern side moldings have a metal insert embedded in one part of the molding to suppress expansion and contraction of the molding due to outside temperature.

The insert is coated with a urethane-based, cleobrene-based, acrylonitrile-butadiene-based adhesive, or the like, in order to be bonded to the resin forming the molding.

However, these adhesives do not have very strong adhesive strength and do not have the adhesive strength to overcome the difference in expansion and contraction between the resin and the insert, so the insert peels off from the resin at an early stage and the insert is exposed to the outside air of the molding. Expansion and condensation due to temperature changes could not be suppressed, and the above-mentioned problems also occurred. Further, after long-term use, the plasticizer, stabilizer, and low-molecular compounds in the molding resin may volatilize, causing the molding to shrink and the insert to protrude from the end of the molding, which may impair the appearance. At present, there is no adhesive suitable for bonding aluminum or iron to PvC, and the above-mentioned problems are particularly likely to occur in PVC moldings in which aluminum or iron inserts are embedded.

In view of the above, an object of the present invention is to provide an adhesive that has adhesive strength that can overcome the difference in expansion and contraction between resin and metal in PVC moldings in which aluminum inserts and iron inserts are embedded. do.

The gist of this invention is (al) polyester diol and diisocyanate having OH groups at both ends are NCO: 0fI = 1: o
.

The urethane (U) obtained by reacting at a molar ratio of 65 to 0.95 is cut into 100 parts by weight to produce acrylonitrile, methacrylonitrol, acrylic acid, acrylic ester, methyl methacrylic acid, and methyl methacrylic ester. Acrylic urethane (A) 100 parts (solid content) obtained by polymerizing one type or a mixture of two or more of these derivatives (solid content) and 100 parts of halogenated polymer, acrylonitrile, One type or a mixture of two or more of methacrylonitrile, acrylic acid, acrylic ester, methyl methacrylic acid, methyl methacrylic ester and their derivatives.
0 to 150 parts are mixed and polymerized, and acrylic... ρ Genated polymer (B) 2 to 50 parts (solid content), IcI rubber vulcanizing agent 5 to 300 parts (solid content), and TDL rubber An adhesive made by dissolving 5 to 300 parts by weight (solid content) of a vulcanization accelerator and 10 to 100 parts (solid content) of +e+ epoxy resin in an organic solvent, and is used to embed aluminum inserts and iron inserts. It is used by applying it to inserts when molding PVC products. The adhesive of the present invention will be explained in more detail below.

This adhesive is made of the above acrylic urethane (A), 5 to 300 parts of a rubber vulcanizing agent, and 5 to 30 parts of a rubber vulcanization accelerator.
0 parts, 2 to 50 parts of acrylic halogenated polymer, and 10 to 100 parts of epoxy resin diluted with an organic solvent. When the urethane ([J) is synthesized, a polyester diol having an OH group at the terminal and a diisocyanate are reacted at a molar ratio of NCO: 0H=1:0.65 to 0.95. When the OH group is 0.65 mol or less, the resulting urethane molecules are small, and the resulting adhesive is sticky and lacks heat resistance. Moreover, if the OH group is 0.95 to 1 mole, the molecular cap of the adhesive becomes high, and when this adhesive is dissolved in a solvent, the solution stability becomes poor and a gelled product is generated partially. In addition, one type or a mixture of two or more of acrylonitrile, methacrylonitrole, acrylic acid, methacrylic acid, acrylic ester, methacrylic ester, and their derivatives is 1 to 100 parts of urethane (TJ).
0 to 50 parts are polymerized. In this case, if the amount is 10 parts or less, the softening point of the adhesive will be low and heat resistance will be lost. Furthermore, the adhesive strength to the metal insert side is also reduced. Also, if the amount is more than 150 parts, the adhesive will become hard, and if the metal/C-sert is bent or folded after being applied, the adhesive will easily peel off from the metal surface at the interface, so use less than 150 parts. is preferred. Furthermore, for every 100 parts of the halogenated polymer, 10 to 150 parts of acrylonitrile, methacrylonitrile, acrylic acid, acrylic ester, methacrylic acid, methacrylic ester, and a mixture of 2,811 or more thereof are added. Partial reaction. If the amount is 10 parts or less, metal ink → no. similar to acrylic urethane (A)
If the adhesive strength to the side is low 1 and is 150 parts or more,
Similar to acrylic urethane (A), the adhesive became hard and the same results were obtained. In addition, by reacting acrylics with halogenated polymers, precipitation of rubber fillers (carbon, white carbon, etc.), rubber vulcanizing agents, rubber vulcanization accelerators, etc. can be significantly prevented. At the same time, the adhesive strength was significantly improved by reacting with acrylics.

Examples of halogenated polymers include chlorides and bromides of polyethylene-polypropylene, ethylene-propylene terpolymer terpolymer, and the like. Vulcanizing agent for rubber,
If the amount of the rubber vulcanization accelerator is 5 parts or less, the adhesive after vulcanization and curing will be soft, will not exhibit adhesive strength, and will have weak adhesive strength to the metal insert side. If the amount is 300 parts or more, the adhesive becomes hard and brittle after vulcanization and curing. Furthermore, if the amount of the epoxy resin is less than 10 parts, the adhesive force to the metal side will be weak, and if it is more than 50 parts, the adhesive force to the PVC side will decrease and at the same time the solution stability of the adhesive will deteriorate, resulting in partial gelation. A monster is formed.

Examples of the organic solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexane, benzene, toluene, xylene, ethyl acetate, isopropyl acetate, and isobutyl acetate. In addition, the above-mentioned vulcanizing agents, vulcanization accelerators, etc. are zinc dimethyldithiocarbamate, zinc dibutyldithiocarbamate, N-ethyl-N-phenyldithiocarbamate, silver dimethyldithiocarbamate, dimethyldithiocarbamate f1M2U, ethyldithiorubamate, tellylurium 2-mercaptobenzothiazole dibenzothia Dil disulfide Tetramethylthiuram disulfide Dipentamethylenethiuram tetrasulfide S Also, anti-aging agent for rubber, if necessary when adjusting the adhesive.
Rubber compounding agents such as plasticizers, rubber softeners, and fillers, such as carbon black and white carbon, may also be added.

In addition, the above epoxy resin is Bisphenol type epoxy resin Allyl glycidyl ether n-butyl glycidyl ether Phenyl glinodylethyl Halogenated bisphenol type X: C1orBr resorcinol type Bisphenol F type Detrahydroxyphenylethane type Borac type epoxy resin Glycerin triether type etc. can be exemplified.

Examples of the polyester diol include polyesters such as polyethylene adipate, polybutylene adipate, and polyethylene butylene adipate.

Examples of diisocyanates include 4,4'-diphenylmethane diisocyanate and tolylene diisoneanate.

Furthermore, examples of acrylonitrile, methacrylonitrile acrylic acid, acrylic ester, methacrylic acid, methacrylic ester and derivatives thereof include acrylic acid,
Methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylheginol acrylate, methoxyethyl acrylate, methyl methacrylate, hequinol methacrylate, decyl octyl methacrylate, lauryl methacrylate, stearyl methacrylate, dimethylaminoethyl methacrylate , methacryleamide, glycidyl methacrylate, isooctyl acrylate, N-n-butoxymethylacrylamide, N-methylolacryl 7mide, N-N-dimethylaminoethyl acrylate, N・N-diethylaminoethyl acrylate-+・, N- Methylaminoethyl acrylate, N-ethylaminoethyl acrylate, Nt-methylaminoethyl acrylate, N.N-dimethylaminopropyl acrylate Next, the polymerization method of this adhesive will be explained.

ta+ Urethane (U) This urethane (U) is a polyester diol and diisoanate having OH groups at both ends, NCO:0H=1:
A mixture of 0.65 to 0.95 molar ratio is dissolved in the above-mentioned organic solvent, mixed, and reacted at 80°C for 3 hours with stirring in dry nitrogen gas to synthesize tb+ Acrylic urethane (A) This acrylic urethane ( A) is urethane (U) 100
Acrylonitrile, methacrylate trile,
Acrylic acid, acrylic ester, methacrylic acid, methacrylic ester or their derivatives at 10 to 150
part, dissolved and mixed in the above-mentioned organic solvent, added a peroxide catalyst such as benzoyl peroxide (hereinafter abbreviated as B, P, 0), and polymerized while stirring at 80 to 85 ° C. for about 5 hours, Synthesize.

tc+ Acrylic halogenated polymer (B) 10 to 150 parts of the above acrylics to 100 parts of halogenated polymer,
B, P, Oo, and os parts were dissolved in the above organic solvent and heated at 80°.
Acrylic halogenated polymer is synthesized by C3Hrs reaction.

Next, a method of using the adhesive having the above structure will be explained.

First, the surface of the aluminum group or iron insert is
After cleaning, the viscosity (80 to 20
The adhesive of the present invention diluted to 00 CPS) is applied to a dry film thickness of 30 to 200 μm. The application method includes
Examples include spray coating, brush coating, knife coating, and roll coating, but these are not specified.

Next, the adhesive layer on the surface of the insert is dried at a temperature ranging from room temperature to 300° C. for several seconds to several tens of minutes. Preferably it is 200°C or less. ? C) If the temperature exceeds 0°C, the adhesive and insert may deteriorate.

Next, by embedding the above-mentioned insert at the same time as PVC molding, a PVC molding containing the required insert can be obtained.

In this way, when the obtained PVC molding is used as a side molding for an automobile, etc., the insert and PVC molding
Even if the molding is subjected to large temperature changes or the plasticizers, stabilizers, etc. in the PVC volatilize, the insert will not peel off from the PVC, so the molding The insert will not bend or the insert will not protrude from the edge of the molding.

Examples of the present invention will be listed below along with comparative examples to confirm the results of the present invention. For each test piece, adhesive was applied onto an iron insert (width 18 mm) by dipping and dried at 200°C for 2 minutes, at which time the adhesive film thickness was 60 mm.
It was ~70 μm.

This insert was extruded from an extruder together with the following PVC compound to create a side molding.

PVC compound PVC 100 parts Dioctyl phthalate 50 parts Calcium carbonate 10 parts Dibutyltin dilaurate
3 parts pigment 1 part Test method The above test piece was tested using a tensile tester (Tensilon UTM-1
-5000W manufactured by Toyo Baldwin),
A 180° peel test was conducted at a tensile speed of 50 mm/win. In addition, in the heat aging test, the test piece was heated to 80°C.
Place it in a thermostat, leave it for 200 hours, and then heat it to 180 degrees at room temperature.
°Peeling test, weather resistance test is carbon arc lamp 2
Sunshine Weatherometer (product name:
This is a 180° peel test at room temperature after exposure for 200 hours at Toyo Rika Kogyo Co., Ltd.). The above test results are shown in Table-
Shown in 1.

In addition, Comparative Example 1 uses NBR adhesive (Bond G103
・In Comparative Example 2, CRR adhesive Bond G17 (trade name, manufactured by Konishi ■) was used.

The adhesives of the Examples of this invention exhibit significantly greater bond strength between PVC and iron than the adhesives of the Comparative Examples.

In particular, rubber adhesives have poor heat resistance and weather resistance.

(, U-1) Urethane polyethylene adipate (molecule i approximately 2000) 3
20 parts 4-4'-diphenylmethane diisocyanate 50 parts 925 parts toluene 7555 parts methyl ethyl keto were added, and the mixture was dried and reacted at 80° C. for 3 hours in nitrogen gas.

(U-2) Urethane polybutylene adipate (molecular weight approximately 2000) 32
0 parts 4,4'-diphenylmethane diisocyanate 50 parts Toluene 925 parts Methyl ethyl ketone 555 parts were added, dried, and reacted in nitrogen gas at 80° C. for 3 hours.

(A-1) 100 parts of urethane of acrylic urethane (U-1), 20 parts of methyl methacrylate, 80 parts of toluene, and 0.05 parts of B and P were added, and a reaction was carried out at 80°C for 5 hours.

(A-2) 100 parts of urethane of acrylic urethane (U-1), 20 parts of ethyl methacrylate, 80 parts of toluene, and 05 parts of B, P, OO were added, and a reaction was carried out at 80°C for 5 hours.

(A-3) 100 parts of urethane of acrylic urethane (U-2), 20 parts of methyl methacrylate, 80 parts of toluene, and parts of B, P, Oo, and Os were added, and a reaction was carried out at 80°C for 5 hours.

(A-4) Acrylic urethane (U-2) 100 parts of urethane, ethyl methacrylate)
20 parts of toluene, 80 parts of toluene, and 0.05 parts of B and P were added, and a reaction was carried out at 80°C for 5 hours.

(B-1) Acrylic halogenated polymer chlorinated rubber 100
parts, 50 parts of methyl methacrylate, 1 part of ncrohexanone
25 parts, 100 parts of toluene, and 0.05 parts of B and P were added, and a reaction was carried out at 80°C for 5 hours.

(B-2) Acrylic halogenated polymer chlorinated rubber 100
parts, 50 parts of ethyl methacrylate, 1 part of nclohexanone
25 parts,) 100 parts of toluene, and 0.05 parts of B and P were added, and a reaction was carried out at 80°C for 5 hours.

Example 1 100 parts of acrylic urethane (A-1), 50 parts of acrylic halogenated polymer (B-1), 10 parts of sulfur, 10 parts of zinc dimethyldithiocarbamate, 20 parts of ZnO, epoxy resin Epicron 850 (jIL184 to epoxy)
190 (trade name, manufactured by Dainippon Ink ■), 15 parts of white carbon, and 30 parts of toluene were mixed to form an adhesive.

Example 2, 100 parts of acrylic urethane (A-2), 50 parts of acrylic halogenated polymer (B-1), 10 parts of sulfur, 10 parts of zinc diethyldithiocarbamate - Epoxy resin Epicron 857 (epoxy equivalent 190-205) Dainippon Ink An adhesive was prepared by mixing 4 parts (trade name, manufactured by ■) and 30 parts of toluene.

Example 3 Acrylic urethane (A-3) 10 o parts, acrylic halogenated polymer (B-1) 50 parts, sulfur 10 parts, white carbon 15 parts, N-ethyl-N-phenyldithiocarbamine [fi lead 10 parts, Zn020 part, epoxy resin Epiclon JSR-960 (epoxy equivalent: 350~
390 Manufactured by Dainippon Ink Part name) 4 parts, toluene 3
0 parts were mixed to form an adhesive.

Example 4 100 parts of acrylic urethane (A-4), 50 parts of acrylic halogenated polymer (B-1), 10 parts of sulfur, 715 parts of phophytocarylE, 20 parts of ZnO, 10 iron dimethyldithiocarbamate M2 epoxy resin Epicune 8
50 (epoxy equivalent: 184-190, trade name, manufactured by Dainippon Ink ■) and 30 parts of toluene were mixed to form an adhesive.

Example 5 100 parts of acrylic urethane (A-1), 50 parts of acrylic halogenated polymer (3-2), 10 parts of sulfur, 10 parts of zinc dimethyldithiocarbamate, 20 parts of Zn0, 15 parts of white carbon, epoxy [m Epicron 850 (
An adhesive was prepared by mixing 4 parts of epoxy Jl 184-190 (trade name, manufactured by Dainippon Ink ■), 15 parts of white carbon, and 30 parts of toluene.

Table-1 unit = (kg/cm) Patent and patent applicant: Toyoda Gosei Co., Ltd.

Claims (1)

[Claims] +a+ Polyester diol and diisocyanate having OH groups at both terminals are NCO: OH2I: 0.65~
Urethane tut10 obtained by reacting at a molar ratio of 0.95
50 to 150 parts by weight of one or a mixture of two or more of acrylonitrile, methacrylonitrole, acrylic acid, methacrylic acid, acrylic esters, methacrylic esters, and derivatives thereof can be polymerized based on 0 parts by weight (solid content). Acrylic urethane (4) ioo parts by weight (solid content)
and tb+ 10 to 50 parts by weight of acryl tetranitrol, methacrylonitrol, acrylic acid, methacrylic acid, methacrylic ester, acrylic ester, and a mixture of two or more of their derivatives to 100 parts by weight of the halogenated polymer.
2 to 50 parts by weight (solid content) of the acrylic halogenated polymer (B) obtained by mixing and polymerizing parts by weight at °C, 5 to 300 parts by weight (solid content) of a vulcanizing agent for rubber, and 5 parts of a vulcanization accelerator for rubber. ~300 parts by weight (solid content) and tel epoxy resin 10 to 300 parts by weight (solid content)
An adhesive for inserts used in polyvinyl chloride products dissolved in an organic solvent.