TWI498406B - Adhesive and adhesive method - Google Patents

Description

Adhesives and adhesives

The present invention relates to an adhesive member and a bonding method, and more particularly to an adhesive member for bonding an unvulcanized rubber to a dissimilar material having a polar surface, and a bonding method using the bonding member.

In the industry, complicated processing steps are often required to effectively closely bond dissimilar materials together. For example, when rubber (non-polar material) is bonded to other dissimilar materials, the surface of the rubber is easily oxidized, or the processing aid (for example, processing oil, processing wax, etc.) migrates to the rubber surface. The nature of the rubber surface is unstable, which in turn adversely affects subsequent bonding to dissimilar materials. Therefore, in order to reduce the instability of the surface properties of the rubber, and to avoid affecting the subsequent bonding effect, the rubber will first perform a series of surface treatments before the bonding. Taking the conventional rubber surface treatment process as an example: the surface of the vulcanized rubber is roughened by mechanical means to increase the contact area at the time of bonding and simultaneously expose the unoxidized portion, and then the surface of the vulcanized rubber is further treated with a treating agent. The treatment is followed by an adhesive and then applied to a dissimilar material having a polar surface.

Patent EP1323800A2 discloses an application in shoe assembly The adhesive film comprises a polar bonding layer formed of thermoplastic polyurethanes and a non-polar bonding layer formed of an ethylene copolymer, and the polar bonding layer can be adhered to a material to be attached The non-polar bonding layer can be adhered to a non-polar material to be attached, so that the adhesive material can adhere the non-polar material to be attached to the non-polar material to be attached. However, the above-mentioned adhesive film has a problem that the non-polar bonding layer and the polar bonding layer have poor compatibility with each other, and the two bonding layers may not be closely adhered to each other, and when the bonding film is used for bonding, It may cause the object to be attached to the polar material to be attached to the non-polar material to be attached. Further, the ethylene copolymer (e.g., ethylene-vinyl acetate copolymer) forming the nonpolar bonding layer has a problem of insufficient heat resistance.

Accordingly, a first object of the present invention is to provide an adhesive member which can improve the problem of poor compatibility of the above-mentioned polar bonding layer with a non-polar bonding layer.

Thus, the adhesive of the present invention comprises an adhesive film. The adhesive film comprises a first adhesive layer and a second adhesive layer disposed on the first adhesive layer, wherein the first adhesive layer is formed by hardening a polyurethane composition, and the polyurethane composition contains polyurethane a hardener, an interfacial compatibilizer, and the second adhesive layer are formed of a rubber composition comprising a rubber component, and an interfacial compatibilizer, the interface compatibilizer of the polyurethane composition and The interface compatibilizer of the rubber composition is the same or different, and the interface compatibilizer has at least one double bond and at least one polar group.

A second object of the present invention is to provide a viscous method, Adhesive The adhesive is used to bond an unvulcanized rubber to a dissimilar material having a polar surface.

Thus, the adhesive method of the present invention comprises: providing a bond as described above a second adhesive layer of the adhesive member is attached to the unvulcanized rubber and subjected to a heat pressing treatment to cause a bridging reaction between the second adhesive layer and the unvulcanized rubber; and the first in the adhesive member An adhesive layer is attached to the heterogeneous material having a polar surface and subjected to a press-bonding treatment.

The effect of the invention is that the adhesive of the invention is used for making one a dissimilar material having a polar surface bonded to an unvulcanized rubber, the first adhesive layer being capable of bonding to the dissimilar material having a polar surface, the second adhesive layer being capable of bonding with the unvulcanized rubber, and because of the interface compatibilizing agent The first adhesive layer and the second adhesive layer have good compatibility, and through the adhesive member of the present invention, the heterogeneous material having the polar surface can be well adhered to the unvulcanized rubber, and the adhesion between the two is improved. strength.

The adhesive method of the invention uses the adhesive member to make an unvulcanized rubber When it is bonded to a dissimilar material having a polar surface, not only the unvulcanized rubber but also the dissimilar material having a polar surface can be well bonded, and the laminating operation flow can be shortened.

As used herein, the unvulcanized rubber refers to a rubber that contains a bridging agent but which does not undergo a bridging reaction to produce a sulfurized crosslink. The types of rubber are, for example but not limited to: natural rubber, chloroprene rubber, styrene butadiene rubber, nitrile rubber, polyiso Ethylene rubber, butadiene rubber, EPDM or a combination thereof, and the vulcanizing agent is adjusted depending on the rubber type. The dissimilar material having a polar surface, the "heterologous material" refers to a material other than the rubber, and is not limited to a polar material or a non-polar material, and may be formed into a polar surface after surface treatment, preferably The polar surface is coated with a layer of polyurethane glue. The heterogeneous material having a polar surface such as, but not limited to, a polyurethane having a polar surface.

The adhesive member of the invention comprises: an adhesive film and a bonding film A superposed release film.

The adhesive film includes a first adhesive layer, and one is disposed on the first a second adhesive layer on the adhesive layer, wherein the first adhesive layer is formed by hardening a polyurethane composition comprising a polyurethane, a hardener, an interfacial compatibilizer, and the second adhesive layer Formed by a rubber composition comprising a rubber component and an interfacial compatibilizer, the interface compatibilizer of the polyurethane composition being the same or different from the interfacial compatibilizer of the rubber composition, and The interfacial compatibilizer has at least one double bond and at least one polar group.

Preferably, the polar group is selected from the group consisting of a hydroxyl group, an ester group, and an ether. , an isocyanurate group, an allophanate group, a biuret group, a N-acylurea group, a urethane group (urethane group), urea group (urea group), uretdione group, iminooxadiazindione group, carbodiimide group, Isocyanate group, epoxy group, nitrile group, A chloro group, a phenyl group, a carbonate ester group, or a combination thereof.

The adhesive member of the invention enables a dissimilar material having a polar surface Adhesive to an unvulcanized rubber, a first adhesive layer formed of a polar polyurethane composition can be bonded to the heterogeneous material having a polar surface, and a second adhesive layer formed of a non-polar rubber composition can be bonded to the unvulcanized rubber.

The polyurethane composition and the rubber composition will be further improved below. Step description.

Polyurethane Composition

Preferably, the crystalline melting temperature range of the polyurethane composition From 30 ° C to 70 ° C, the heat of fusion of the crystal ranges from 20 J/g to 55 J/g [The above properties are measured by a differential scanning calorimeter (DSC) at the first temperature rise, and the heating rate is 10 ° C / Min.]. The polyurethane composition includes a polyurethane, a hardener, and an interfacial compatibilizer, each of which will be further described below in the polyurethane composition.

[polyurethane]

The polyurethane may be in a solvent type or a water dispersion type. Preferably, the polyurethane has a crystalline melting temperature in the range of from 30 ° C to 70 ° C.

Preferably, the polyurethane comprises 80 wt% to 90 wt% of a soft segment, and the soft segment has 80 wt% to 100 wt% based on the total amount of the soft segment of 100 wt% Polyester. The polyester is, for example but not limited to, (1). It is obtained by polymerizing adipic acid with a mono diol compound such as, but not limited to, ethylene glycol, propylene glycol, 1,4-butanediol, 1,6- Hexanediol, Neopentyl glycol, 2-methyl-1,3-propanediol, diethylene glycol or dipropylene glycol, etc., the above diol compounds can be used singly or in combination. (2). Polycaprolactone; or (3). (1) and (2). More specifically, the polyester is, for example but not limited to, poly(1,4-butylene adipate, PBA for short), polyethylene adipate-1 ,4-butylene glycol ester [poly(ethylene-1,4-butylene adipate), referred to as PEBA], poly(ethylene adipate), abbreviated as PEA, or poly(adipate) [poly(hexamethylene-neopentyl adipate), referred to as PHNA].

The polyurethane can be prepared by a general method, such as diol It is obtained by carrying out polymerization reaction with diisocyanate. Preferably, the polyurethane may be a modified polyurethane such as a polyurethane containing an unsaturated group such as, but not limited to, a vinyl group, an allyl group, an acrylate group, or a methacrylate group. Base. The above unsaturated group may be located on the main chain of the polyurethane, the side chain, the pendant group of the main chain, or the terminal group of the main chain. When the polyurethane is a polyurethane containing an unsaturated group, the unsaturated group of the unsaturated group-containing polyurethane reacts with the double bond contained in the rubber component.

[hardener]

The hardener may be selected from any hardener suitable for use with a polyurethane. Preferably, the hardener is a water dispersible polyisocyanate. The hardener is, for example but not limited to, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), toluene diisocyanate (TDI), diphenylmethane diisocyanate (diphenylmethane diisocyanate (TDI), diphenylmethane diisocyanate (TDI) Diphenylmethane diisocyanate, MDI), or 4,4'-dicyclohexylmethane diisocyanate (H ₁₂ MDI), etc.; the above hardener optionally further contains at least one of the following groups: A polyisocyanate group, an allophanate group, a biuret group, an amine ester group, a uretdione group, an imidodiazepinene quinonedione group, and a carbodiimide group. More specifically, the hardener is, for example but not limited to, HDI trimer isocyanate, IPDI trimer isocyanate, HDI/IPDI trimer isocyanate or allophanate-containing HDI. The above various hardeners may be used singly or in combination.

Preferably, the hardener has an average functional group number ranging from 2.5 to 4.5, more preferably from 3.0 to 4.2.

When the polyurethane composition is prepared, the hardener can be directly mixed with other components, or dissolved in a common organic solvent and then mixed with other components.

The hardener can increase the adhesion between the first adhesive layer and the dissimilar material having the polar surface, thereby increasing the bonding strength of the dissimilar material having the polar surface after bonding with the unvulcanized rubber. Preferably, the hardener is used in an amount ranging from 0.5 to 9.0 parts by weight based on 100 parts by weight of the total of the polyurethane. The amount of the hardener used is less than 0.5 parts by weight, which may cause insufficient mechanical strength of the first adhesive layer, and may cause peeling of the first adhesive layer and the dissimilar material having the polar surface. If the amount of the hardener is more than 9.0 parts by weight, the adhesion of the first adhesive layer to the dissimilar material having a polar surface is disadvantageous. More preferably, the hardener is used in an amount ranging from 1 to 7.5 parts by weight.

[Interface compatibilizer]

Preferably, the interfacial compatibilizer is selected from the group consisting of triallyl isocyanurate, tris (hydroxymethyl) propane trimethacrylate, and pentaerythritol triene. Pentaerythritol triallyl ether, zinc dimethacrylate, pentaerythritol triacrylate, pentaerythritol propoxylate triacrylate, unsaturated aliphatic urethane acrylate Commercially available products such as Desmolux ^® U 100 manufactured by Bayer Co., Ltd., Isocyanate-bearing aliphatic urethane acrylate (commercially available as Desmolux ^® XP 2510 manufactured by Bayer Co., Ltd.), hydroxyl terminated polybutadiene [hydroxyl-terminated polybutadiene, commercially available as manufactured by the company Cray Valley Krasol ^® series] or a combination of these. It is worth mentioning that the interface compatibilizer improves the compatibility between the first adhesive layer and the second adhesive layer by: (1) the double bond contained in the interface compatibilizer and the rubber group The double bond produces a bridging reaction; (2) the polar group of the interfacial compatibilizer and the polar group of the polyurethane form a bond or van der Waals.

Preferably, the total weight of the polyurethane is 100 parts by weight, The amount of interfacial compatibilizer is in the range of 0.5 to 4 parts by weight. When the amount of the interface compatibilizer exceeds 4 parts by weight, the degree of crosslinking of the first adhesive layer is lowered, so that the strength of the first adhesive layer is insufficient. More preferably, the interface compatibilizer is used in an amount ranging from 0.5 to 3 parts by weight.

[starting agent]

An initiator may also be optionally added to the polyurethane composition. The initiator can be used singly or in combination, such as, but not limited to, t-butyl peroxy-2-ethylhexyl monocarbonate, 1,1-di (tertiary) 1,1,1-di(t-butylperoxycyclohexane), dicumyl peroxide, 2,5-dimethyl-n-hexane-2,5-dihydroperoxide 2,5-dimethylhexane 2,5-dihydroperoxide.

The initiator can enable dissimilar materials with polar surfaces and unsulfurized The rubber has a good adhesion strength after being applied to the water and washed. Preferably, the initiator is used in an amount ranging from 0 to 5 parts by weight based on 100 parts by weight of the total of the polyurethane. More preferably, the initiator is used in an amount ranging from 0.1 to 3 parts by weight.

The preparation of the polyurethane composition is not particularly limited, for example,

The components described above are placed in a stirrer and stirred uniformly.

Rubber Composition

The rubber composition includes a rubber component and an interface compatibilizer. Take Each component in the rubber composition will be further described below.

[Rubber component]

The rubber component is selected to match the unvulcanized rubber. It is to provide excellent adhesion between the second adhesive layer and the unvulcanized rubber. The rubber component is, for example but not limited to, the following types: natural rubber (NR), chloroprene rubber (CR), butylbenzene Styrene-butadiene rubber (SBR), nitrile rubber (nitrile-butadiene rubber, NBR), polyisoprene (IR) or polybutadiene (BR). In addition to the rubber of the above kind, the rubber component may be selected from a rubber grafted or modified with a polar compound, and a Chlorinated rubber obtained by a chlorine-based modification. The rubber grafted or modified with the polar compound is, for example, a chloroprene rubber grafted or modified with a polar compound or a natural rubber grafted with a polar compound such as, but not limited to, methyl methacrylate (methyl methacrylate, MMA), maleic anhydride (MAH), hydroxyethyl methacrylate (HEMA), or N-hydroxyethyl acrylamide, carboxylic acid Base. More specifically, the rubber grafted or modified with the polar compound is, for example but not limited to, methyl methacrylate-grafted natural rubber, methyl methacrylate-grafted chloropyrene rubber, and the like. The above types of rubber may be used singly or in combination.

[Interface compatibilizer]

The interfacial compatibilizer in the rubber composition is the same as described above and will not be described again.

The interface compatibilizer is used in an amount ranging from 1 to 15 parts by weight based on 100 parts by weight of the total of the rubber component. When the amount of the interface compatibilizer is more than 15 parts by weight, the heat resistance of the second adhesive layer is deteriorated, and the second adhesive layer is also liable to have a color.

Additives such as a bridging agent, an activator, a vulcanization accelerator, a tackifier, or an antioxidant may be optionally added to the rubber composition. The details of each additive are as follows: [Bridge agent]

In the subsequent bonding process, the bridging agent can bridge the second adhesive layer with the unvulcanized rubber, and bond between the second adhesive layer and the unvulcanized rubber, thereby increasing the gap between the second adhesive layer and the unvulcanized rubber. The degree of adhesion. The bridging agent is selected depending on the nature of the rubber component and can be used singly or in combination. The bridging agent is preferably a compound having a half-life temperature higher than 90 ° C after ten hours of use. Preferably, the bridging agent is selected from the group consisting of sulfurs or peroxides.

Preferably, the bridging agent is used in an amount ranging from 0 to 6 parts by weight based on 100 parts by weight of the total of the rubber component. More preferably, the bridging agent is used in an amount ranging from 1 to 3 parts by weight.

It should be particularly noted here that since the bridging agent contained in the unvulcanized rubber migrates to the surface of the unvulcanized rubber during the bonding, even when the rubber composition does not contain a bridging agent, the second adhesive layer and the The bridging reaction still occurs between the unvulcanized rubber, so that the second adhesive layer and the unvulcanized rubber adhere well.

[activator]

An activator (vulcanization activator) can be selectively added depending on the nature of the rubber composition and subsequent requirements. The active agent is a reagent capable of promoting the bridging reaction. The selection and dosage of the active agent are adjusted depending on the type and amount of the rubber composition or the unvulcanized rubber, and the type and amount of the bridging agent. In a specific example of the adhesive of the present invention, the activator is, for example but not limited to, ZnO, MgO or polyethylene glycol, and the above activators can be used singly or in combination. Preferably, the total weight of the rubber component is 100 parts by weight, the activity The amount of the agent used is in the range of 2 to 10 parts by weight.

[Sulfurization accelerator]

The vulcanization accelerator is used to increase the degree of bridging reaction between the second adhesive layer and the unvulcanized rubber. The selection and dosage of the vulcanization accelerator are adjusted depending on the type and amount of the rubber composition or the unvulcanized rubber, and the type and amount of the bridging agent. The vulcanization accelerator can be used singly or in combination, such as, but not limited to, guanidines, aldehyde-amines, aldehyde-ammonias, thioureas, thiurams. Thiurams, xanthates, sulphenamides, dithiocarbamates, or thiazoles. Preferably, when the vulcanization accelerator is used in combination of two or more kinds, a preferable bonding strength can be obtained.

Preferably, the vulcanization accelerator is used in an amount ranging from 0.1 to 3 parts by weight based on 100 parts by weight of the total of the rubber component.

[tackifier]

The tackifier can improve the contact viscosity between the second adhesive layer and the unvulcanized rubber, thereby improving the adhesion between the second adhesive layer and the unvulcanized rubber. The tackifier can be used singly or in combination, such as but not limited to: rosin, rosin derivatives, modified or unmodified terpene resins, aliphatic petroleum resins, cycloaliphatic petroleum resins. , or aromatic petroleum resin. It is preferred that the above-mentioned modified or unmodified terpene resin, aliphatic petroleum resin, cycloaliphatic petroleum resin, and aromatic petroleum resin have a polar functional group.

Preferably, the total weight of the rubber component is 100 parts by weight, The tackifier is used in an amount ranging from 1 to 40 parts by weight. If the amount of the tackifier is more than 40 parts by weight, the toughness of the second adhesive layer is lowered, and the color is easily carried.

[Antioxidants]

The antioxidant is used to improve the stability of the second adhesive layer. The antioxidant can be used singly or in combination, such as, but not limited to, 2,6-di-tert-butyl hydroxytoluene (BHT), and sebacic acid bis(1,2,2,6,6-five Methyl-4-piperidinyl) [bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate], or azelaic acid methyl 1,2,2,6,6-penta Methyl 4-piperidyl ester (methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate).

Preferably, the antioxidant is used in an amount ranging from 0.05 to 2 parts by weight based on 100 parts by weight of the total of the rubber component.

The preparation of the rubber composition is not particularly limited. For example, the above components may be placed in a stirrer and stirred uniformly.

Release film

The release film can be in contact with the first adhesive layer or in contact with the second adhesive layer. In a preferred embodiment of the adhesive of the present invention, the first adhesive layer and the second adhesive layer are respectively separated from each other. Type film contact. The material of the release film is not particularly limited, and examples thereof include, but are not limited to, polyethylene terephthalate (PET), polypropylene (PP), polyethylene (PE), and polytetrafluoroethylene. In a specific example of the adhesive of the present invention, the release film is polyethylene terephthalate.

The adhesive of the present invention is prepared by coating the polyurethane composition After the release film is dried, to form the first adhesive layer, and then coating the rubber composition on the first adhesive layer, and drying to form the second adhesive layer, and then The adhesive layer of the present invention is obtained by covering the second adhesive layer with another release film.

The adhesive of the present invention makes the first adhesive layer because of the interface compatibilizer It is compatible with the second adhesive layer and is well adhered to each other, and the adhesive member of the present invention can effectively match the dissimilar material having the polar surface with the unvulcanized rubber, and simultaneously improve the bonding of the two. Then the intensity. At the same time, the adhesive material of the invention has a wide range of dissimilar materials, and is not limited to a polar material, and is also suitable for a non-polar material having a surface having a surface after surface treatment, and thus is of great help to industrial applications.

The subsequent application of the adhesive of the present invention is not particularly limited as long as It is suitable for the application of the unvulcanized rubber and the dissimilar materials having a polar surface (for example, footwear, construction, packaging, sports equipment, etc.) to use the adhesive of the present invention. A particular application of the adhesive of the present invention is the conforming assembly of the shoe assembly, more specifically the bonding of the outsole (unvulcanized rubber) to the midsole (a dissimilar material having a polar surface).

The adhesive method of the invention is used for making an unvulcanized rubber and a Dissimilar materials with polar surfaces are bonded. The adhesive method comprises: after removing the above-mentioned adhesive member from the release film on the second adhesive layer, bonding the second adhesive layer to the unvulcanized rubber and performing a heat pressing treatment to make the second adhesive A bridging reaction occurs between the layer and the unvulcanized rubber. The release film is removed from the first adhesive layer, and the first adhesive layer is attached to the heterogeneous material having a polar surface and subjected to a press-bonding treatment. Preferably, the first adhesive layer is attached to the The dissimilar material having a polar surface is subjected to a heat activation treatment to thermally activate the first adhesive layer to a surface temperature of 60 ° C or higher, and then the first adhesive layer is attached to the dissimilar material having a polar surface.

Preferably, the hot pressing treatment has a hot pressing temperature ranging from 120 ° C to 180 ° C, a hot pressing pressure ranging from 100 kg/cm ² to 150 kg/cm ² , and a hot pressing time ranging from 4 minutes to 6 minutes.

Preferably, the press-bonding treatment has a press-fit temperature in the range of 25 ° C to 40 ° C, a press-fit time in the range of 8 seconds to 30 seconds, and a pressure in the range of 20 kg/cm ² to 40 kg/cm ² .

The adhesive method of the present invention is made in the process of the hot pressing process The bridging reaction between the vulcanized rubber and the second adhesive layer causes a bond between the two to enhance the adhesion between the two, so that it is not necessary to perform a complicated surface treatment on the rubber as in the conventional case, and then the subsequent bonding process can be performed. Therefore, the operational flow of the fit can be effectively simplified.

The invention will be further illustrated by the following examples, but It is to be understood that the examples are for illustrative purposes only and are not to be construed as limiting.

<Example>

The following examples and comparative examples were prepared using the following materials, respectively:

1. Polyurethane: Dadong 71 (solvent type polyurethane, soft segment content ranging from 80 wt% to 90 wt%) manufactured by Dadong Resin Co., Ltd., and Dadong 6608 (water-dispersed polyurethane) with a soft segment content of 80 Wt% to 90 wt%).

2. Hardener: Dadong 367S (polyisocyanate hardener) manufactured by Dadong Resin Co., Ltd., and Dadong 368 (polyisocyanate hardener) were used.

3. Interfacial compatibilizer: TAIC (trylyl tripolyisocyanate) manufactured by Acros, PETA (pentaerythritol triacrylate) manufactured by Aldrich, PEPTA (pentoxytetramethylene triacrylate) Pentaerythritol propoxylate triacrylate), and Desmolux ^® XP 2510 (isocyanate-bearing aliphatic urethane acrylate) manufactured by Bayer.

4. Starting agent: 79C [1,1-di(t-butylperoxy)cyclohexane] manufactured by NOF, Japan.

5. Rubber component: natural rubber (ADS-XL manufactured by Rubbertex Co., Ltd., NR in Tables 1 and 2), styrene-butadiene rubber (SBR1502 manufactured by LG Corporation, and SBR in Table 1 and Table 2), Polyisoprene rubber (SKI-3S manufactured by Sterlitamak Co., Ltd., represented by IR in Tables 1 and 2), Chloroprene rubber (CR570 and G-40 manufactured by TOSOH Co., Ltd., and CR in Tables 1 and 2) Methyl methacrylate grafted natural rubber (self-synthesized, represented by MMA-g-NR in Tables 1 and 2), methyl methacrylate-grafted chloropyrene rubber (self-synthesis, in Tables 1 and 2) MMA-g-CR), and chlorinated rubber (S-20 manufactured by Bayer, indicated by Chlorinated rubber in Tables 1 and 2)

6. Activator: Zinc oxide and polyethylene glycol are used.

7. Bridging agent: 79C manufactured by NOF, Japan.

8. Sulfurizing accelerator: TS (tetramethylthiuram monosulfide) manufactured by Sovereign, and TBBS [N-tert-butyl-benzothiazole-sulfenamide (N-tert-) Butyl-2-benzothiazole sulfenamide)].

9. Tackifier: A rosin resin and a hydrogenated resin manufactured by Arakawa Co., Ltd. were used.

[Example 1] Preparation and adhesion of adhesive parts

The polyurethane composition of Example 1 was prepared according to the types and amounts of the components of Table 1. The polyurethane component, the hardener, the initiator, and the interfacial compatibilizer were placed in a 120 L batch reactor and stirred at 25 ° C. The polyurethane composition of Example 1 was prepared in a uniform state for 15 minutes.

The rubber composition of Example 1 was prepared according to the types and amounts of the components of Table 1. The solvent, the rubber component, the activator, the interfacial compatibilizer, the vulcanization accelerator, and the tackifier were put into a batch of 200 L in the following order. In the secondary reactor, when the temperature of the batch reactor is lowered to 30 ° C, the bridging agent is further added, followed by stirring and dispersing to a uniform state at 60 ° C, and the above-mentioned feeding to stirring process lasts for 8 hours, that is, The rubber composition of Example 1 was obtained.

The coating of the polyurethane composition and the rubber composition was carried out using a continuous comma coater coating machine. The polyurethane composition of Example 1 was applied onto a release film [manufactured by Sigma, Polyethylene terephthalate (PET), film thickness: 25 to 38 μm], and dried. Treatment to harden the polyurethane composition Drying, drying temperature: 80-90-100 ° C), that is, forming a first adhesive layer (film thickness: 25 to 50 μm). Next, after the rubber composition of Example 1 was dissolved in a mixed solvent (100 wt% based on the total weight of the mixed solvent, the mixed solvent contained 38 wt% of a hydrocarbon solvent (hydrocarbon solvent was DSP80/100 manufactured by Exxonmobil Co., Ltd.) , 23 wt% of methylcyclohexane, 17 wt% of n-propyl acetate, and 22 wt% of methyl ethyl ketone, and the total weight of the mixed solvent is 100 wt%, and the amount of the rubber composition ranges from 17 wt% to 22 wt%), coated on the first adhesive layer, dried (staged drying, drying temperature: 70-80-90 ° C), that is, a second adhesive layer (film thickness: 25 to 50 μm) is formed. Then, another release film was covered on the second adhesive layer, that is, the adhesive of Example 1 was obtained.

The second adhesive layer of the adhesive of Example 1 was brought into contact with the unvulcanized rubber to be bonded (the type of unvulcanized rubber: a mixture of BR, IR, NBR and SBR), and placed in a hot press (brand type: Daejeon Oil Pressure 01EA- 10) performing a hot pressing treatment so that the second adhesive layer is bonded to the unvulcanized rubber to be bonded and a bridging reaction occurs, and the hot pressing treatment conditions are: temperature 120 ° C to 180 ° C, pressure 150 kg / cm ² , time 5 minute. After the hot pressing process is completed, the release film is removed, and the first adhesive layer is brought into contact with an EVA to be attached with a polar surface, followed by pressing treatment, and the pressing treatment condition is: pressure 30 kg/cm ² , time 10 seconds That is, the adhesion of Example 1 was completed, and a bonded sample (indicated in Table 1 as: rubber-bonded EVA) was obtained. The EVA-attached article having a polar surface was replaced with a nylon-attached article having a polar surface, the above-mentioned adhesion method was repeated, and another bonded sample (indicated as: rubber-bonded Nylon in Table 1) was obtained.

[Examples 2 to 12 and Comparative Examples 1 to 4] Preparation of Adhesives And sticky

In Examples 2 to 12 and Comparative Examples 1 to 4, an adhesive member was prepared in the same manner as in Example 1, and the adhesion was carried out in the same manner and a bonded sample was obtained.

The types and amounts of the components in Examples 1 to 12 and Comparative Examples 1 to 4 are shown in Tables 1 and 2.

[evaluation project]

1. Then the strength test

The bonded samples of the above Examples 1 to 12 and Comparative Examples 1 to 4 were subjected to the adhesion strength test in accordance with ASTM D-1876.

Rubber-bonded EVA: The strength is 7 kg/in or more.

Rubber-bonded Nylon: The subsequent strength of 9 kg/in or more indicates pass.

2. Interface compatibility test

The position of the fracture surface of the bonded samples of Examples 1 to 12 and Comparative Examples 1 to 4 after the above-mentioned adhesion strength test was visually observed, and the fracture surface was located on the surface where the first adhesive layer and the second adhesive layer were in contact with each other, and the interface was compatible. The result of the sex test is expressed as ×. If the damage surface is on the surface of rubber, EVA (or Nylon), or the surface of the first adhesive layer that is bonded to EVA (or Nylon), or the surface of the second adhesive layer that is bonded to the rubber, the interface compatibility test results indicate ○.

3. Wash test

The bonded samples (rubber-bonded EVA) of Examples 1 to 12 and Comparative Examples 1 to 4 were washed with an Electrolux Wascator water washing machine at a water temperature of 50 ° C for 8 hours, and after washing with water, a sample to be laminated was set at 25 °C dry After 16 hours of drying, the strength test was performed in accordance with ASTM D-1876. After washing with water, the rubber was bonded to EVA: the strength was then 5.2 kg/in or more.

4. Heat resistance test

Heat resistance test: The bonded samples of Examples 1 to 12 and Comparative Examples 1 to 4 (rubber-bonded EVA, size 2.54 cm x 10 cm) were placed in a thermostatic tester (manufacturer model: Chengjia Instrument CJ-6012, tested) Conditions: temperature: 70 ° C, load 1 kg) for 5 hours, observe the sample after 5 hours. The crack between the rubber and the EVA is 0 cm to 1.5 cm, and the heat resistance test result indicates ○. The rubber is completely separated from the EVA, and the heat resistance test result indicates ×.

Add to.

The results of Tables 1 and 2 show that the adhesive members of Comparative Examples 1 to 4 have an interface separation between the first adhesive layer and the second adhesive layer due to the absence of the use of the interface compatibilizing agent in the polyurethane composition and the rubber composition. And the adhesion strength of the bonded samples is less than good.

In contrast, in the adhesive members of Examples 1 to 12, since the interface compatibilizing agent was used, the interface between the first adhesive layer and the second adhesive layer did not occur, and the adhesive strength of the bonded sample was excellent.

In addition, the adhesives of Example 1, Examples 3 to 5 and Examples 7 to 12 have excellent heat resistance due to the use of the initiator, and can maintain good after washing. strength.

In summary, the adhesive of the present invention has good compatibility between the first adhesive layer and the second adhesive layer due to the use of the interface compatibilizing agent, and can improve the bonding of the unvulcanized rubber to the dissimilar material having the polar surface. Then the intensity. The adhesive method of the present invention, in combination with the above-mentioned adhesive member, not only allows the unvulcanized rubber to adhere well to the dissimilar material having a polar surface, but also shortens the laminating operation process.

The above is only the preferred embodiment of the present invention, and the scope of the present invention is not limited thereto, that is, the simple equivalent changes and modifications made by the patent application scope and patent specification content of the present invention, All remain within the scope of the invention patent.

Claims (9)

A viscous method for bonding an unvulcanized rubber to a dissimilar material having a polar surface, the viscous method comprising: providing an adhesive member, wherein the adhesive member comprises an adhesive film, the adhesive film comprising a first An adhesive layer, and a second adhesive layer disposed on the first adhesive layer, wherein the first adhesive layer is formed by hardening a polyurethane composition comprising a polyurethane, a hardener, and an interface phase The container, and the second adhesive layer are formed of a rubber composition containing a rubber component, and an interface compatibilizing agent, an interface phase of the polyurethane composition and an interface of the rubber composition The agent is the same or different, and the interface compatibilizer has at least one double bond and at least one polar group; the second adhesive layer of the adhesive is attached to the unvulcanized rubber and subjected to a heat pressing treatment to A bridging reaction occurs between the second adhesive layer and the unvulcanized rubber; and the first adhesive layer in the adhesive member is attached to the heterogeneous material having a polar surface and subjected to a press-bonding treatment. The adhesive method according to claim 1, wherein the polar group is selected from the group consisting of a hydroxyl group, an ester group, an ether group, a trimeric isocyanate group, an allophanate group, a biuret group, and an N-mercapto urea. Base, urethane group, ureido group, uretdione group, iminodiazepinetriene ruthenium diketone group, carbodiimide group, isocyanate group, epoxy group, nitrile group, chlorine group , phenyl, carbonate group or a combination of these. The adhesive method according to claim 1, wherein the interfacial compatibilizer is selected from the group consisting of triallyl isocyanurate, cis (hydroxymethyl) propane trimethacrylate, pentaerythritol triallyl ether, and Zinc methacrylate, pentaerythritol triacrylate, propoxylated pentaerythritol triacrylate, aliphatic unsaturated urethane amide, aliphatic acrylate containing isocyanate group, hydroxyl terminated polybutadiene or a combination thereof . The adhesive method according to claim 1, wherein the interface compatibilizer is used in an amount ranging from 1 to 15 parts by weight based on 100 parts by weight of the total of the rubber component. The adhesive method according to claim 1, wherein the interface compatibilizer is used in an amount ranging from 0.5 to 4 parts by weight based on 100 parts by weight of the total of the polyurethane. The adhesive method according to claim 1, wherein the rubber composition further contains a bridging agent. The adhesive method of claim 6, wherein the bridging agent is selected from the group consisting of peroxides, sulfur, or a combination of the two. The adhesive method according to claim 1, wherein the hardener is used in an amount ranging from 0.5 to 9.0 parts by weight based on 100 parts by weight of the total of the polyurethane. The adhesive method according to claim 1, wherein the polyurethane composition further contains an initiator.