JP2938591B2 - Adhesive composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a modular window molding method in which an adhesive having an excellent initial adhesive strength at the time of heat, in particular, a sheet glass is placed in a mold and a molding made of vinyl chloride resin is integrally molded by injection molding. The present invention relates to an adhesive composition used in the above.

[0002]

2. Description of the Related Art Conventional adhesive compositions of this kind include the following. (b) Thermoplastic polyurethane resin 122 (parts by weight) (c) Epoxy resin with hydroxyl group 50〃 (e) Organic solvent 946〃 (f) Curing agent 15〃

[0003]

However, in such a conventional adhesive composition, since the initial adhesive strength of the adhesive at the time of heating is insufficient, vinyl chloride is formed in the cavity space in the modular window molding step. Inject resin,
When the plate glass integrated with the molding is removed from the mold after solidification, there is a problem that the molding is peeled off due to shrinkage of the molding or by an external force applied to the molding part.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of such problems, and (a) 70 to 40 parts by weight of a saturated polyester resin; (b) thermoplastic polyurethane resin 10
(C) 15 to 30 parts by weight of an epoxy resin having a hydroxyl group, (d) 4 to 10 parts by weight of a silane coupling agent, (e) 200 to 1000 parts by weight of an organic solvent, and (f) a curing agent 5 The present invention relates to an adhesive composition having excellent initial adhesive strength when heated, characterized by comprising up to 40 parts by weight.

The components used in the adhesive of the present invention will be described below. The saturated polyester resin as the component (a) includes polybasic acids such as terephthalic acid, isophthalic acid, phthalic acid, adipic acid, and sebacic acid, and dihydric alcohols such as diethylene glycol, 1,4-butanediol, and 1,6- Hexanediol and neopentyl glycol undergo a condensation reaction,
The resulting polyester resin has a terminal hydroxyl group. The amount of the saturated polyester resin (a) is 70
When the amount exceeds 70 parts by weight, interfacial peeling between the adhesive and the glass occurs. When the amount is less than 40 parts by weight, interfacial peeling between the adhesive and the vinyl chloride resin (PVC) occurs. The thermoplastic polyurethane resin as the component (b) is a resin having a urethane bond in a molecular chain, and is composed of a polybasic acid such as terephthalic acid, isophthalic acid, phthalic acid, succinic acid, adipic acid, sebacic acid, and a dihydric alcohol. For example, a polyester resin or an aromatic polycarbonate resin having a terminal hydrosiloxy group obtained by subjecting ethylene glycol, 1,4-butanediol, 1,6-hexanediol, and neopentyl glycol to a condensation reaction, ε-caprolactone ring-opening polymerization The active hydrogen of a polyester resin such as an isocyanate group such as a diisocyanate compound such as tolylene diisocyanate or diphenylmethane diisocyanate using a suitable known catalyst such as a tertiary amine or stannous chloride. Reacted terminal hydroxyl group poly It is a urethane resin. (b) The compounding amount of the thermoplastic polyurethane resin of the component is 10 to 30 parts by weight, and if it exceeds 30 parts by weight, the interface between the adhesive and the PVC occurs.If it is less than 10 parts by weight, the interface between the adhesive and the glass becomes Peeling occurs. The epoxy resin having a hydroxyl group (c) is a mixture of a condensation product of phenols and epichlorohydrin having at least one epoxy group in one molecule, and is particularly effective in the adhesive of the present invention. Epoxy resins have an average molecular weight of 800-
8,000 epoxy resins with an epoxy equivalent of 450 to 3,500. (c) The amount of the epoxy resin as the component is 15 to 30 parts by weight. Occurs. (d) As the silane coupling agent of the component, a vinyl group,
Methacryl group, epoxy group, amino group, mercapto group,
Or those containing chlorine in the molecule, especially,
Those effective in the present invention are those containing an epoxy group. (d) The compounding amount of the component silane coupling agent is 4 to 10
If the amount is more than 10 parts by weight, the cost becomes high. If the amount is less than 4 parts by weight, peeling of the interface between the adhesive and the glass occurs. (e) Ethyl acetate, methyl ethyl ketone, acetone, cyclohexanone, toluene, xylene and the like are used as the organic solvent as a component. The organic solvent is required to be 200-200 to perform the adhesive manufacturing process and the adhesive
It is preferable to add 1000 parts by weight. As the curing agent of the component (f), any one can be used as long as it has a low vapor pressure, a low toxicity to the human body, and is easy to handle. Solution.
(f) The compounding amount of the curing agent of the component is 5 to 40 parts by weight.
If the amount is less than 5 parts by weight, curing failure of the adhesive occurs, which is not preferable.

When the adhesive composition of the present invention is produced, the component (b) is polymerized at the time of polymerization of the thermoplastic polyurethane resin, that is, at the time of the reaction between the polyester diol and the diisocyanate.
Component (a) is a saturated polyester resin and component (d) is a silane coupling agent to the copolymerized epoxy resin having a hydroxyl group, or component (b) is a homopolymerized thermoplastic polyurethane resin. It is preferable that the product is mixed with a saturated polyester resin as the component (a), an epoxy resin having a hydroxyl group as the component (c), and a silane coupling agent as the component (d). The adhesive used in the present invention is usually the above (a)
It is practically used in the form of an organic solvent comprising an adhesive composition comprising the component, the component (b), the component (c), the component (d) and the component (e) and the curing agent of the component (f).

[0007]

Next, the operation will be described. The adhesive composition of the present invention has an improved initial adhesive strength when heated by blending the above components (a) to (f) in prescribed amounts. It is considered that the causes of the insufficient initial adhesive strength during heating are the following two items. (1) The base material of the adhesive is likely to break due to insufficient strength of the adhesive itself when heated. (2) Low adhesive strength at the interface between the adhesive and the glass plate. The insufficient strength at the time of (1) is that the saturated polyester resin added to the adhesive component is uniformly dispersed as an island in the sea of the copolymer of the thermoplastic polyurethane resin and the epoxy resin when the adhesive is cured. At this time, since the saturated polyester resin has high strength at high temperatures, the strength of the adhesive itself was improved, and it became possible to prevent the base material from being broken. (2) The adhesive strength of the interface between the adhesive and the glass plate was improved by adding a silane coupling agent to the adhesive component.

[0008]

Next, the present invention will be described with reference to examples and comparative examples. Examples 1 and 2 and Comparative Examples 1 and 2 Examples 1 and 2 were prepared using the adhesive components (a) to (e) shown in Table 1.
And the adhesives of Comparative Examples 1 and 2 were manufactured, each adhesive was applied to a plate glass, placed in a mold, and a vinyl chloride resin (PVC) was injected into a cavity space, and module window molding was performed to form a PVC. After solidification, the sheet glass was taken out of the mold, the presence / absence of peeling of the molding immediately after being taken out, and after taking out of the mold, a result of performing a molding hand peeling test under heat is also shown in Table 1.

[0009]

[Table 1]

In Examples 1 and 2, a mixture of a thermoplastic polyurethane and an epoxy resin, a mixture of a saturated polyester resin and a silane coupling agent as an adhesive main component, and a polyisocyanate as a cross-linking agent and 100: A mixture of 2 to 5 by weight is applied as an adhesive to a sheet glass,
After injecting viruny chloride resin into the cavity space and solidifying it, the plate glass was taken out of the mold and subjected to modular window molding. In both examples, there was no peeling of the molding immediately after being taken out of the mold, and in the manual peeling test when heated after being taken out of the mold, the base material of the polyvinyl chloride resin of the molding was broken. In Comparative Example 1, since the added amount of the silane coupling agent was small, there was no effect, and peeling of the molding immediately after being taken out of the mold was observed. And glass interfacial peeling was observed. In Comparative Example 2, since the amount of the saturated polyester resin added was small, there was no effect, and peeling of the molding immediately after being taken out of the mold was observed. Fracture and interfacial fracture between adhesive and PVC were observed. The following components were used as the components (a) to (d) shown in Table 1.

Component (a) Saturated polyester resin (amorphous) Dicarboxylic acid: A mixture of terephthalic acid and adipic acid, sebacic acid, etc. Diol: 1,4-butanediol, 1,6-hexanediol, diethylene glycol and Mixture of neopentyl glycol, etc. Hydroxyl value: 5 to 8 (mg KOH / g) Acid value: 1 to 3 (mg KOH / g) Number average molecular weight: about 20,000 (b) Component: polyurethane resin diisocyanate: tolylene diisocyanate (TDI) Polyester dicarboxylic acid: a mixture of sebacic acid, isophthalic acid, {number average molecular weight}, adipic acid, etc. Approximately 2,000 diol: A mixture of ethylene glycol, neopentyl glycol, 1,6-hexanediol, etc. Diol (chain extender): 1,6-hexanediol (c) component: epoxy resin bisphe Condensation product of phenol A and epichlorohydrin Average molecular weight: 800 to 900 Epoxy equivalent: 450 to 500 (d) Component: Silane coupling agent γ-glycidoxypropyltrimethoxysilane (e) Component: Organic solvent Acetic acid Polar solvents such as ethyl, methyl ether ketone, acetone, and cyclohexanone are necessary for dissolving the compounded resin, and toluene and xylene are used in combination for adjusting the drying rate and preventing moisture absorption. (f) Component: curing agent triisocyanate phenyl thiophosphate
10-40% solution

Examples 3 and 4 and Comparative Examples 3 and 4 Examples 3 and 4 were conducted using the adhesive components (a) to (e) shown in Table 2.
Then, the adhesives of Comparative Examples 3 and 4 were manufactured, and module window molding was performed in the same manner as in Example 1. After the molded glass sheet was removed from the mold immediately after removal from the mold, and after removing from the mold, the sheet glass was heated. Table 2 also shows the results obtained by performing the mall hand peel test.

[0013]

[Table 2]

In Examples 3 and 4, a mixture of a thermoplastic polyurethane resin homopolymer, a saturated polyester resin, an epoxy resin having a hydroxyl group and a silane coupling agent was used as the main component of the adhesive, and the curing agent polyether was used. A mixture of isocyanate and 100: 2 to 5 in a weight ratio is applied as an adhesive to a plate glass, placed in a mold, PVC is injected into the cavity space, and after solidification, the plate glass is taken out of the mold. Modular window molding. In both Examples 3 and 4, the same results as in Example 1 were obtained. The result of Comparative Example 3 was the same as that of Comparative Example 1, and the result of Comparative Example 4 was the same as that of Comparative Example 2.

[0015]

As described above, the adhesive composition of the present invention comprises a prescribed amount of (a) a saturated polyester resin,
(b) a thermoplastic polyurethane resin, (c) an epoxy resin having a hydroxyl group, (d) a silane coupling agent, (e) an organic solvent, and (f) a curing agent, thereby improving initial adhesive strength during heating, This adhesive is applied to the sheet glass, placed in a mold, and solidified polyvinyl chloride resin is injected into the cavity space. After solidification, the mold can be prevented from peeling after removing the sheet glass from the mold. , Improved long-term durability, 50
As a result of a hand peel test after leaving in a constant temperature and humidity oven at 95 ° C and 95% RH for 240 hours, the base material of the mall was destroyed.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-2-187486 (JP, A) JP-A-2-84482 (JP, A) JP-A-58-122977 (JP, A) (58) Investigation Field (Int.Cl. ⁶ , DB name) C09J 167/02 C09J 163/00 C09J 175/04 C08G 59/40 C08L 63/00

Claims (1)

(57) [Claims] (1) 70 to 40 parts by weight of a saturated polyester resin, (b) 10 to 30 parts by weight of a thermoplastic polyurethane resin, (c)
15 to 30 parts by weight of an epoxy resin having a hydroxyl group, (d) 4 to 10 parts by weight of a silane coupling agent, (e) 200 to 1000 parts by weight of an organic solvent, and (f) 5 to 40 parts by weight of a curing agent. An adhesive composition having an excellent hot initial adhesive strength.