JPS624772A - Mold mounting structure - Google Patents

Abstract

PURPOSE:To prevent a mold from being peeled from an adherend, by using a specified pressure-sensitive adhesive contg. a polyester polyurethane for a double-coated adhesive tape as an adhesive to be applied to at least the adherend side in mounting a mold on an adherend such as an automobile body, a bumper, etc. through a double-coated adhesive tape. CONSTITUTION:A mold 2 is mounted on an adherend 1 through a double-coated adhesive tape 6. The following pressure-sensitive adhesive for the double-coated adhesive tape 6 is used as an adhesive 3 to be applied to at least the adherend side 1. Said adhesive is one member of a mixture (a) of a polyester polyurethane contg. an isocyanate or hydroxyl group at its terminal and at least one member selected from polyacrylic acid derivatives or polymethacrylic acid derivatives, or a polymer (b) composed of a polyester polyurethane contg. an isocyanate or hydroxyl group at its terminal and an acrylic acid derivative monomer or a methacrylic acid derivative monomer.

Description

DETAILED DESCRIPTION OF THE INVENTION Object of the Invention (Field of Industrial Application) The present invention relates to a mounting structure for a molding mounted on the body, bumper, etc. of an automobile.

(Prior art) Automobile bodies and bumpers are made of synthetic resin or synthetic rubber, especially vinyl chloride resin or E.
PDM (ethylene-propylene-diene ternary copolymer rubber), EPM (ethylene-propylene copolymer rubber)
A molding made of polyolefin vulcanized rubber such as

A molding that is attached to the side of the body and has the function of preventing scratches from contact with other objects when opening a door, etc., and also as a decoration is called a side protection molding, and is attached to the body using double-sided tape. .

Therefore, it is easy to install, and there is no need to drill holes in the body, so there is no rust.

The above-mentioned double-sided tape has a base material made of sponge, nonwoven fabric, film, paper, etc. formed into a thin plate of material such as acrylic rubber, polyethylene, or chloroprene rubber, and butylene acrylate coated on both sides of the base material. , butyl methacrylate, 2-ethylhexyl acrylate, and other acrylic adhesives.

(Problems to be Solved by the Invention) However, problems with the mold made of vinyl chloride resin include repeated contraction and expansion due to temperature differences between day and night, summer and winter, and low molecular weight in the mold. Double-sided tapes are affected by various factors such as shrinkage due to volatilization of compounds, and shrinkage due to plasticizers and stabilizers in the molding decomposing and becoming low molecular due to interaction with heat, light, moisture, etc., and shrinkage due to these volatilizing in the air. It has been pointed out that peeling is likely to occur between the tape and the molding or between the double-sided tape and the body.

In addition, a problem with molds made of EPDM, EPM, etc. is that these polyolefin vulcanized rubbers do not contain polar groups in the main chain of their molecules, so paints, adhesives, adhesives, etc. It has been pointed out that even when applied, the adhesion of the resulting coating film is insufficient, and peeling is likely to occur between the double-sided tape and the molding or between the double-sided tape and the body.

As a result of repeated research into the mounting structure of the molding for the purpose of solving the above-mentioned problems, the present inventor found that the above-mentioned vinyl chloride resin,
Alternatively, the present invention was achieved by discovering an adhesive that has strong adhesion to molds made of polyolefin vulcanized rubber such as EPDM and EPM.

Structure of the Invention (Means for Solving Problems) The present invention provides a structure in which a molding is attached to an adherend via a double-sided tape, in which the adhesive on at least the adherend side of the double-sided tape is (a ) A mixture of a polyester polyurethane having an isocyanate group or a hydroxyl group at the end and at least one of a polyacrylic acid derivative or a polymethacrylic acid derivative, or a polyester polyurethane having an isocyanate group or a hydroxyl group at the end. and a polymer comprising at least one of an acrylic acid derivative monomer or a methacrylic acid derivative monomer.

(Function) With the above means, the adhesion of the molding to the adherend is significantly improved compared to the stress caused by the expansion and contraction of the molding caused by the various factors mentioned above, thereby preventing the molding from peeling off from the adherend.

(Example) Hereinafter, the composition of the adhesive used in the molding mounting structure of the present invention will be explained in detail.

First, polyester polyurethane with isocyanate groups at the terminals is a polyurethane obtained by adding diisocyanate and polyester polyol in a molar ratio such that the diisocyanate is in excess and reacting in dry nitrogen gas according to a conventional method. , where the diisocyanate includes tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hydrogenated 4,4'-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, xylene diisocyanate, hydrogenated xylene diisocyanate, isophorone diisocyanate and 1.6
-Hexamethylene diisocyanate can be exemplified.

Furthermore, polyester polyol is a polyester composed of an organic acid and a polyol, and examples of the organic acid include phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, succinic acid, adipic acid, azelaic acid, and sebacic acid. be able to.

In addition, as polyols, ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, 1,5-bentanediol, 1 , 6-hexanediol, neopentyl glycol, 2.2.4-1-
Dimethylbencune-1,3-diol, hydrogenated bisphenol A1 trimethylene glycol and 2-ethyl-1
An example is 3-hexanediol.

The molecular weight of the polyester polyurethane having isocyanate groups at the terminals is 500 to 5,000, more preferably 1,000 to 3,000; if it is less than 500, the adhesive will be hard and brittle, and if it exceeds 5,000, it will be too soft. In either case, the adhesion strength decreases.

In addition, the solvents used when preparing the above polyurethane are benzene, toluene, xylene, n-hexane, cyclohexane, methyl ethyl ketone, methyl isopropyl ketone,
It is one kind of solvent selected from methyl isobutyl ketone, methyl acetate, ethyl acetate, isopropyl acetate, and isobutyl acetate, or a mixed solvent of two or more kinds.

Next, polyester polyurethane with hydroxyl groups at the terminals is obtained by adding the above-exemplified isocyanate and polyester polyol in a molar ratio such that the polyester polyol is in excess, and reacting in dry nitrogen gas according to a conventional method. The molecular weight of the polyurethane is preferably in the range of 500 to 5,000, more preferably 1,000 to 3,000 for the reasons mentioned above.

The above-mentioned polyester polyurethane having isocyanate groups or hydroxyl groups at the terminals may be mixed with at least one kind of polyacrylic acid derivative or polymethacrylic acid derivative, or mixed with at least one kind of acrylic acid derivative monomer or methacrylic acid derivative monomer. Polyacrylic acid derivatives include methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, 1s
Acrylic acid derivative monomers such as o-butyl acrylate, isodecyl acrylate, lauryl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate and dimethylaminoethyl acrylate; acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid; Obtained by polymerizing acid, citraconic acid, citraconic anhydride, itaconic acid, itaconic anhydride, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, and other active hydrogen-containing compounds according to a conventional method. It is a polymer.

In addition, polymethacrylic acid derivatives include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, 1so-butyl methacrylate, isodecyl methacrylate, lauryl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, It is a polymer obtained by polymerizing a methacrylic acid derivative monomer such as dimethylaminoethyl acrylate and the active hydrogen-containing compound listed above according to a conventional method.

Here, the mixing ratio of the polyester polyurethane having isocyanate groups or hydroxyl groups at the terminals and the polymer made of at least one of polyacrylic acid derivatives or polymethacrylic acid derivatives may be arbitrary, but preferably the ratio of polyester polyurethane is 5-95% (
weight ratio).

Further, the solvent used in the mixing is the various organic solvents exemplified as the solvent used in preparing the polyurethane.

Next, a polymer consisting of a polyester polyurethane having an isocyanate group or a hydroxyl group at the end and at least one of an acrylic acid derivative monomer or a methacrylic acid derivative monomer is prepared by adding benzoyl peroxide, di-2- Using a polymerization initiator such as ethylhexyl peroxydicarbonate or di-3-methoxybutyl peroxydicarbonate, a polyester polyurethane having an isocyanate group or a hydroxyl group at the terminal and having the above-mentioned composition according to a conventional method, and an acrylic It is a polymer obtained by carrying out a polymerization reaction with at least one type of acid derivative monomer or methacrylic acid derivative monomer under conditions such that the proportion of polyester polyurethane is in the range of 5 to 95% (weight ratio).

Next, specific examples of the composition and preparation method of the adhesive will be explained.

(Hereinafter, all parts are parts by weight) Adhesive-1 6584.28 parts of toluene and 658 parts of methyl ethyl ketone
Hydrogenated 4°4'-diphenylmethane diisocyanate (MDI) 1048.
76 parts, 2000 parts of polybutylene adipate (PBA, molecular weight approximately 2000) and 243.38 parts of 1,4-butanediol (BD) as a chain extender were added, and a polymerization reaction was carried out at 80°C for 3 hours in dry nitrogen gas. I went and got polyurethane.

Next, a copolymer of n-butyl acrylate and maleic anhydride (acid value = 20 to 25) was diluted with a mixed solvent of toluene/cyclohexane/ethyl acetate = 1/1/1 (weight ratio) to obtain a solid content of 37. % solution (hereinafter referred to as Acrylic-A
A pressure-sensitive adhesive was prepared by mixing 95 parts of the above-mentioned polyurethane with 5 parts of the above-mentioned polyurethane.

Adhesive-2 5840.76 parts of toluene and 584 parts of methyl ethyl ketone
In a mixed solvent consisting of 0.76 parts of xylene diisocyanate (XD I), 752.76 parts of polyethylene adipate (PEA, molecular weight = approximately 2000), 2000 parts of polyethylene adipate (PEA, molecular weight = approximately 2000)
and ethylene glycol (EG) as a chain extender.
Add 167.62 parts and heat at 80°C in dry nitrogen gas for 3
A time polymerization reaction was performed to obtain polyurethane.

Next, a copolymer of n-butyl acrylate and fumaric acid (acid value = 30 to 32) was mixed into toluene/cyclohexane/
An adhesive was prepared by mixing 90 parts of a solution (hereinafter referred to as Acrylic-B) with a solid content of 37% diluted with a mixed solvent of ethyl acetate = 1/1/1 (weight ratio) and 10 parts of the above polyurethane.

For all of the following adhesives 3 to 16, isocyanate and polyester are diluted with a mixed solvent of toluene/methyl ethyl ketone = 1/1 (weight ratio) so that the solid content is 20%, and this is diluted with dry nitrogen gas. The reaction was carried out at 80°C for 3 hours in a dry nitrogen gas atmosphere after adding a chain extender.
: Prepared by mixing polyurethane obtained by reaction at 80° C. for 1 hour and a polymer made of at least one of polyacrylic acid derivatives and polymethacrylic acid derivatives.

Adhesive-3 Polyurethane: MD 1100 parts, PEA (molecular weight = 4
00) 53.26 parts, EG14.05 parts.

Copolymer of acrylic-Can-butyl acrylate and 2-hydroxyethyl methacrylate (OH number = 54
~58) was diluted with a mixed solvent of toluene/cyclohexane/ethyl acetate-1/1/1 (weight ratio) to give a solid content of 37%.

Mixing ratio: polyurethane/acrylic-C=15/85°Adhesive-4 Polyurethane: MD1100 parts, PBA (molecular weight=5
00) 66.56 parts, 1,4-butanediol (BD)
20.40 copies.

Copolymer of acrylic-Den-butyl acrylate and 2-hydroxypropyl methacrylate (OH number = 2
6 to 30) were diluted with a mixed solvent of toluene/cyclohexane/ethyl acetate=1/1/1 (weight ratio) to give a solid content of 37%.

Mixing ratio: polyurethane/acrylic-D=20/80°Adhesive-5 Polyurethane: MD 1100 parts, polyethylene butylene adipate (PBA: molecular weight = 2000) 266.31
parts, 26.76 parts of 1,6-hexanediol (HD).

Mixing ratio: polyurethane/acrylic-A=30/70°Adhesive-6 Polyurethane: MD1100 parts, PEA (molecular weight=5
000) 665.78 parts, EG14.05 parts.

Mixing ratio: Polyurethane/Acrylic-A=35/65°Adhesive-7 Polyurethane: MD1100 parts, PBA (molecular weight=6
000) 798.93 copies, BD 20.40 copies.

Mixing ratio: Polyurethane/acrylic-A = 40/60□ Adhesive-8 Polyurethane: 1100 parts of XD, PEA (molecular weight = 1
000) 191.94 parts, EC44.09 parts.

Mixing ratio: polyurethane/acrylic-A = 50150° Adhesive-9 Polyurethane: 1100 parts of XD, PEA (molecular weight = 20
00) 383.88 copies, EC44.09 copies.

Mixing ratio: polyurethane/acrylic-A = 60/40° Adhesive-10 Polyurethane: hydrogenated MD 1100 parts, polyethylene azelate (PEAz: molecular weight = 1000) 127.06
Department, EC29, 20th Department.

Mixing ratio: polyurethane/acrylic-A=70/30°Adhesive-11 Polyurethane: 1.6 100 parts of hexamethylene diisocyanate (HMDI), polyethylene sebacate (PE
Se: molecular weight = 1000) 99.1 parts, EC28.9
Part 2.

Mixing ratio: polyurethane/acrylic-A = 80/20° Adhesive-12 Polyurethane: MD 1100 parts, PEA (molecular weight = 1
000) 266.31 parts, EC 5.79 parts.

Mixing ratio: Polyurethane/Acrylic-A = 90/10° Adhesive-13 Polyurethane: MD 1100 parts, PEA (molecular weight = 1
000) 199.80 copies, EGlo, 54 copies.

Mixing ratio: polyurethane/acrylic-A = 90/10° Adhesive-14 Polyurethane: MD 1100 parts, PEA (molecular weight = 1
000) 299.70 copies, EGo, 69 copies.

Mixing ratio: polyurethane/acrylic-B=50150°Adhesive-15 Polyurethane: MD1100 parts, PEA (molecular weight=1
000) 159.87 parts, EC13.40 parts.

Mixing ratio: polyurethane/acrylic-〇=50150゜Adhesive-16 Polyurethane: MD1100 parts, PEA (molecular weight=1
000) 133.16 parts, EC15.29 parts.

Combination ratio: polyurethane/acrylic-D=50150°Adhesive-17 MDI 750.78 parts, PEA (molecular weight=2000)
2000 parts, BD 198.31 parts polyurethane and polymethyl methacrylate (PMMA) 1224.2
9 parts.

Mixing ratio: polyurethane-PMMA mixture/acrylic-B
= 50150° Adhesive-18 Hydrogenated MDI 786.57 parts, PBA (molecular weight = 200
0) Polyurethane and polymethyl acrylate (PMA) 2392, consisting of 2000 parts, EC130, 37 parts.
56 parts.

Mixing ratio: polyurethane-PMA mixture/acrylic-c=
50150°Next, the following adhesives-19 to 28 are made by reacting isocyanate and polyester at 80°C in dry nitrogen gas for 3 hours, then adding a chain extender and reacting again at 80°C in dry nitrogen gas.
After reacting at ℃ for 1 hour, acrylic acid derivative monomer or methacrylic acid derivative monomer and benzoyl peroxide (BPO) as a polymerization catalyst were added at a ratio of 0.01 part to 100 parts of polyester polyurethane made of the above isocyanate and polyester. was added, and the polymerization reaction was further carried out at 80° C. for 8 hours.

Adhesive-19 MDI 100 parts, PEA (molecular weight = 400) 53.26
parts, EC18, 19 parts, methyl methacrylate-1-(MM
A) 1 7 1.4 2 parts.

Adhesive-20 MDI 100 parts, PBA (molecular weight = 50 (]) 66.
58 parts, BD 26.41 parts, ethyl methacrylate (EMA) 19 2.9 sea.

Adhesive-21 MDI 100 parts, PEBA (molecular weight = 2000) 26
6.31 parts, 1,6-hexanediol (HD) 34.
63 copies, MMA 400.91 copies.

Adhesive-22 MD I 100 parts, PEA (molecular weight = 5000) 6
65.78 parts, EC18.19 parts, methyl acrylate (MA) 783.94 parts.

Adhesive-23 MD I 100 parts, PBA (molecular weight = 6000) 7
98.93 parts, BD 26.41 parts, ethyl acrylate (EA) 925.31 parts.

Adhesive-24 MD I 100 parts, PEBA (molecular weight = 2000)
266.31 parts, EC26.41 parts, ethyl acrylate (EA) 925.31 parts.

Adhesive-25 MDI 100 parts, PBA (molecular weight = 1000) 99,
90 copies, BD 28.82 copies, MMA 1925.31 copies.

Adhesive-26 MD I 100 parts, PBA (molecular weight = 3000) 2
39.81 copies, EC20.84 copies, EMA1925°3
Part 1.

Adhesive-27 MD 1100 parts, PEA (molecular weight = 2000) 177.
15 parts, EC28, 59 parts, MMA1528°77 parts.

Adhesive-28 MD I 100 parts, PEBA (molecular weight = 2000)
266.31 parts, EC18, 19 parts, MMA2306.
81 copies.

In addition, the following adhesives -29 to 33 are made by reacting isocyanate and polyester in dry nitrogen gas at 80°C for 3 hours, then adding acrylic acid derivative monomer or methacrylic acid derivative monomer, and benzoyl peroxide (BPO) as a polymerization catalyst. was added at a ratio of 0.01 part to 100 parts of polyester polyurethane consisting of the above-mentioned isocyanate and polyester, and a polymerization reaction was further carried out at 80° C. for 8 hours.

Adhesive-29 MD I I O 0 parts, PEA (, molecular weight = 3000
) 1498, 50 parts, 799.25 parts of MMA/EMA=1/2 formulation.

Adhesive-30 MD 1100 parts, PEA (molecular weight = 2000) 959,
23 parts, MMA/EMA=1/1 formulation 1059.2
Part 3.

Adhesive-31 MD I 100 parts, PEA (molecular weight = 1000) 4
61.74 parts, MMA/EMA=2/1 formulation 113
2.03 parts.

Adhesive-32 MD 1100 parts, PF, A (molecular weight = 1000) 456
．． 62 copies, MA=1669.83 copies.

Adhesive-33 MDI 100 parts, PEA (molecular weight-1000) 449
, 55 copies, EA=1648.66 copies.

Next, an example of a molding mounting structure using each of the above adhesives will be described with reference to the drawings.

In this embodiment, a molding 2 manufactured by extrusion molding of vinyl chloride resin is attached to a car through a double-sided tape 6 coated with an adhesive 3.4 on both sides of a base material 5 made of a 5 times polyethylene foam. It is attached to a body, that is, a steel plate adherend 1 coated with acrylic paint.

The adhesive 4 applied to the molding 2 side of the base material 5 is a conventionally known acrylic adhesive, while the adhesive 3 on the adherend 1 side is the adhesive-1. The molding 2 was made by extrusion molding a vinyl chloride resin having the composition shown in Table 1 at 170°C.

Table 1 (The parts in the table are parts by weight.) In the above example, a well-known acrylic adhesive was used as the adhesive 4 on the molding 2 side of the base material 5, but the molding mounting structure of the present invention is not limited to the above embodiments, and a structure using a well-known urethane adhesive, chloroprene adhesive, or any of the adhesives-1 to 33 above may be adopted instead of the acrylic adhesive. good.

Tests conducted to confirm the adhesion of Adhesives-1 to 33 and their results will be described below.

Test method: Adhesive-1 was applied to the back side of the molding 2 made of vinyl chloride resin used in the above examples, and air-dried for 30 minutes at room temperature.

In addition, after extrusion molding the EPDM compound having the composition shown in Table 2, 1
Adhesive-1 was similarly applied to the back side of the molding made of EPDM produced by vulcanization at 60° C. for 30 minutes, and air-dried at room temperature for 30 minutes.

Next, the adhesive-coated surfaces of these moldings were stacked on top of each other and allowed to stand at room temperature for 3 days, after which a shear test was conducted at a tensile speed of 30 m/min.

Table 2 Similar tests were also conducted using adhesives 2 to 33, and the results shown in Tables 3 and 4 were obtained.

Table-3 Table-4 From the above test results, the shear strength of Adhesives-1 to 33 is as follows:
It was found that the molding made of vinyl chloride resin or EPDM has sufficient strength when used in a structure to be attached to an automobile body.

Therefore, Adhesives-1 to 33 are not limited to the above-mentioned molding attachment structure, but can also be used generally when attaching synthetic resin materials to metals or other adherends.

Effects of the Invention As detailed above, the present invention exhibits the effect of significantly improving the adhesion between the body and the molding when it is used when attaching a molding made of vinyl chloride resin, EPDM, etc. to an automobile body. This is an excellent invention as a molding mounting structure.

[Brief explanation of drawings]

The figure is a sectional view showing an embodiment in which a molding made of vinyl chloride resin is attached to an automobile body as an adherend. 1. Adherent, 2. Molding, 3. Adhesive. Patent applicant Toyoda Gosei Co., Ltd. agent
Patent attorney Hironobu Onda

Claims (1)

[Claims] 1. The molding (2) is attached to the adherend (1) with double-sided tape (
6), the adhesive (3) on at least the adherend (1) side of the double-sided tape (6) is (a) a polyester polyurethane having an isocyanate group or a hydroxyl group at the end; , a mixture consisting of at least one of a polyacrylic acid derivative or a polymethacrylic acid derivative, or (b) a polyester polyurethane having an isocyanate group or a hydroxyl group at the terminal, and at least one of an acrylic acid derivative monomer or a methacrylic acid derivative monomer. A polymer consisting of
A molding mounting structure comprising any one of the following.