JP2003327938A - Hot-melt adhesive for interior automotive trim - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an excellent hot-melt adhesive for interior automotive trim, capable of being used in coating the trim by using a spiral spray or a roll coater, preventing a fogging phenomenon, and having a high deodorizing effect on odors in a cabin. <P>SOLUTION: This hot-melt adhesive for the interior automotive trim is obtained by mixing (B) a tackifier resin in an amount of 50-800 pts.wt. and (C) a liquid hydrocarbon having a melt viscosity of of ≤55,000 mPa.s at 100°C in an amount of 50-300 pts.wt. into (A) a styrene-isoprene-styrene block copolymer, a styrene-butadiene-styrene block copolymer, a hydrogenated product of the styrene-isoprene-styrene block copolymer, and/or a hydrogenated product of the styrene-butadiene-styrene block copolymer in an amount of 100 pts.wt., wherein components having a molecular weight of ≤400 are contained in the hot-melt adhesive in an amount of <7 wt.% based on the total amount of the mixed materials (A), (B), and (C). <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hot-melt adhesive, and more particularly to a hot-melt adhesive which has very little fogging phenomenon when used for bonding interior materials of automobiles.

[0002]

2. Description of the Related Art Conventionally, in order to bond automobile interior materials, a film-like hot melt adhesive is sandwiched between the adherends and hot pressed, or a hot melt adhesive is applied to the surface of one adherend by beading. A method has been adopted in which, after being applied in a tongue shape, it is immediately adhered to the other adherend. Hot melt adhesives used in these methods can be prepared using raw materials that do not contain low molecular weight components, so the components of the adhesive adhere to the inner wall of the windshield or the like to cause fogging in the closed room of the automobile. The so-called fogging phenomenon was not a problem. However, when an adhesive type hot melt adhesive capable of sticking and adhering a large area of adherends to each other after applying a spiral spray or roll coater is used, the fogging caused by the adhesive component is used. Phenomena were always present.

[0003]

SUMMARY OF THE INVENTION The present invention has been made to improve the above-mentioned circumstances, and a spiral spray,
A hot-melt adhesive that can be applied to a wide area evenly by atomization spray or roll coater and then viscously adhered, and has very little fogging phenomenon after the adhered member is installed in an automobile. The purpose is to The above and other objects and novel characteristics of the present invention will be apparent from the following description of the present specification.

[0004]

The present invention provides (A) styrene-isoprene-styrene block copolymer, styrene-butadiene-styrene block copolymer, styrene-
Hydrogenated product of isoprene-styrene block copolymer and / or hydrogenated product of styrene-butadiene-styrene block copolymer 100 parts by weight of (B) tackifying resin 50 to 800 parts by weight, and (C) 100 ° C. Melt viscosity at 55,000 mPa · s
The following liquid hydrocarbons are mixed in an amount of 50 to 300 parts by weight, and the ratio of components having a molecular weight of 400 or less in the total composition (A), (B) and (C) is less than 7% by weight. The present invention relates to a hot melt adhesive for automobile interior materials. Further, the present invention provides (D) 100 parts by weight of a polyolefin-based resin or a hydrogenated product of a polyolefin-based resin and a styrene-isoprene-styrene block copolymer and / or a hydrogenated product of a styrene-butadiene-styrene block copolymer. On the other hand, (B) 50-800 parts by weight of tackifying resin, and (C) a melt viscosity at 100 ° C. of 55,000 mPa · s.
The following liquid hydrocarbons are compounded in an amount of 0 to 100 parts by weight, and the ratio of the components having a molecular weight of 400 or less in the total composition (D), (B) and (C) is less than 7% by weight. The present invention relates to a hot melt adhesive for automobile interior materials.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.

The styrene-isoprene-styrene block copolymer in the above-mentioned component A used in the present invention is commonly called SIS type thermoplastic elastomer, and as a commercial product, Quintac manufactured by Nippon Zeon Co., Ltd. 34
21, Quintac 3433N, Quintac 352
0, Quintac 3450, Quintac 3460, Quintac 3620, and the like. The styrene-butadiene-styrene block copolymer is commonly called SBS type thermoplastic elastomer, and commercially available products include Toughprene A, Tuffprene 125, Asaprene T-420 and Asaprene T manufactured by Asahi Kasei Corporation. -431, Asaprene T-432 and the like. Further, the hydrogenated product of the styrene-isoprene-styrene block copolymer and the hydrogenated product of the styrene-butadiene-styrene block copolymer are respectively known as SEPS thermoplastic elastomer and SEBS thermoplastic elastomer. The commercially available products are Kraton G-1650, Kraton G-1652, and Kraton G manufactured by Shell Chemical Co., Ltd.
-1657, Seplaton 2002, Septon 2043, Septon 2063, Septon 2007 and the like manufactured by Klera. The weight average molecular weight of each block of these copolymers is 2,000 to 125,000 for a styrene block,
Butadiene or isoprene block is 10,000
It is preferably from 0 to 250,000, and the total weight of styrene blocks is from about 10 to the total weight of the copolymer.
It is preferably within the range of 50%.

The polyolefin resin in the above-mentioned component D used in the present invention is commonly called an amorphous polyalphaolefin, and commercially available products include Ubetak UT2304 and Uvetak UT23 manufactured by Ube Industries, Ltd.
30, Ubetac UT2535, Ubetac UT258
5, Ubetac UT2715, Ubetac UT273
0, Hüls Vestplast 708, Vestplast 520, and Vestplast 750. The hydrogenated product of the styrene-isoprene-styrene block copolymer and the hydrogenated product of the styrene-butadiene-styrene block copolymer in the component D used in the present invention are the same as those exemplified in the component A. Things can be used.

In the present invention, in consideration of the spiral spray coatability and the adhesive performance associated therewith, it is preferable to use the component A, and in particular, the SIS thermoplastic elastomer or the SIS thermoplastic elastomer and the SBS thermoplastic resin. Combination with elastomer or SEPS
A thermoplastic thermoplastic elastomer or a combination of a SEPS thermoplastic elastomer and a SEBS thermoplastic elastomer is preferable in the present invention, and in consideration of roll coatability and accompanying adhesive performance, it is a polyolefin of component D. It is preferable to use a styrene-isoprene-styrene block copolymer hydrogenated product or a styrene-butadiene-styrene block copolymer hydrogenated product in combination with a polyolefin resin alone or a polyolefin resin.
In this case, the mixing ratio of the polyolefin resin and the hydrogenated product of the styrene-isoprene-styrene block copolymer or the hydrogenated product of the styrene-butadiene-styrene block copolymer is 100 parts by weight / 0 parts by weight to 70 parts by weight. Part / 30 parts by weight is preferable.

Examples of the tackifying resin as the component B used in the present invention include rosin-based resins, terpene-based resins and petroleum resin-based resins. Examples of the rosin type include natural rosin, polymerized rosin and derivatives thereof such as pentaerythritol ester rosin, glycerin ester rosin and hydrogenated resins thereof, and specifically, commercially available gum rosin, wood rosin and ester. Gum AAL, Ester gum H, Benzel AD, Super
Ester A-100 (above, manufactured by Arakawa Chemical Co., Ltd.) and the like.
Further, as the terpene-based resin, polyterpene-based resin,
There are terpene phenol-based resins and hydrogenated resins thereof, and specific examples thereof include YS resin, YS Polystar T, and Clearon (manufactured by Yasuhara Chemical Co., Ltd.) as commercial products. Further, as the petroleum resin type, there are aliphatic petroleum resin, aromatic petroleum resin, copolymer petroleum resin, hydrogenated petroleum resin and the like. Specifically, as commercially available products, Escorets (Tonen Petrochemical Co., Ltd. Made), Hi-Lets, Tuck Ace, FTR (made by Mitsui Chemicals), Quinton (made by Zeon Corporation), Alcon (made by Arai Chemicals), Japan Neopolymer
(Made by Nippon Oil Co., Ltd.), I-map (made by Idemitsu Oil Co., Ltd.), Marcarets (made by Maruzen Oil Co., Ltd.) and the like. The tackifying resin as the B component can increase the adhesive property to the adherend. The blending amount of the tackifying resin is 50 to 800 parts by weight, preferably 50 to 750 parts by weight, and the blending amount is less than 50 parts by weight, relative to 100 parts by weight of the component A or D. Adhesion to the adherend cannot be obtained, and conversely, if it exceeds 800 parts by weight, the cohesive force of the adhesive force will decrease, and therefore the adhesive force may decrease, and thereby the durability may decrease. .

10 as the C component used in the present invention
Liquid hydrocarbons having a melt viscosity at 0 ° C. of 55,000 mPa · s or less include paraffin-based, naphthene-based, liquid resin-based, and synthetic rubber-based hydrocarbons. Paraffin-based and naphthene-based liquid hydrocarbons are called synthetic rubber extenders or process oils, and process oils include Shelf Rex (manufactured by Shell Chemical Co., Ltd.), Diana process oil (manufactured by Idemitsu Kosan Co., Ltd.), Daimalon, YS oil, rubber soft (manufactured by Yasuhara Chemical Co., Ltd.), fluid paraffin and the like are commercially available. Examples of the liquid resin type include aromatic hydrocarbon type petroleum type high boiling point fractions. Further, the synthetic rubber type includes polybutene, polyisobutylene, poisoprene, polybutadiene and hydrogenated products thereof, and specifically, cuprene LIR, hydrogenated LIR (manufactured by Kuraray Co., Ltd.), tetrax (Japan). Petrochemical Co., Ltd.), Idemitsu Polybutene (Idemitsu Petrochemical Co., Ltd.), Vistanek (Exxon Chemical Co., Ltd.) and the like. The hydrocarbon has a melt viscosity of 55,000 mPa · s at 100 ° C.
If it exceeds, it becomes solid and not preferable. The melt viscosity of the liquid hydrocarbon at 100 ° C. is preferably 1 to 55,0.
It is 00 mPa · s. The liquid hydrocarbon as the C component can reduce the melt viscosity of the adhesive, improve the fluidity during melt coating, improve the tackiness, and increase the adhesive strength. The blending amount of the liquid hydrocarbon is 50 to 300 parts by weight, preferably 100 to 250 parts by weight with respect to 100 parts by weight of the component A, and the blending amount is less than 50 parts by weight, Adhesiveness is insufficient and sufficient adhesion to the adherend cannot be obtained. On the other hand, when it exceeds 300 parts by weight, the cohesive force of the adhesive decreases and it is difficult to obtain adhesiveness. As the component D, a polyolefin resin alone or a mixture of a polyolefin resin and a hydrogenated product of a styrene-isoprene-styrene block copolymer and / or a hydrogenated product of the styrene-butadiene-styrene block copolymer is used. In that case, the blending amount of the liquid hydrocarbon is in the range of 0 to 100 parts by weight with respect to 100 parts by weight of the D component, and even if the blending amount is 0 parts by weight, by selecting the composition of the polyolefin resin, However, there is no problem because the adhesive force and the adhesive force can be obtained, and conversely, when it exceeds 100 parts by weight, it is difficult to obtain a sufficient adhesive force because the cohesive force of the adhesive decreases.

In the present invention, when forming a hot melt adhesive, the ratio of components having a molecular weight (weight average molecular weight, hereinafter the same) of 400 or less in all the blends of (A), (B) and (C). It is blended so as to be less than 7% by weight. Also, (D),
Even when (B) and (C) are blended, the (D),
The components (B) and (C) are blended so that the ratio of the components having a molecular weight of 400 or less is less than 7% by weight. In particular, the tackifying resin and the melt viscosity at 100 ° C are 55,000 m.
When a liquid hydrocarbon of Pa · s or less is used, these tackifying resins and the melt viscosity at 100 ° C. are 55,000 m.
A liquid hydrocarbon having a molecular weight of 400 or less is selectively blended so that the ratio of components having a molecular weight of 400 or less is less than 7% by weight.
Particularly preferably, from the tackifying resin and the liquid hydrocarbon having a melt viscosity at 100 ° C. of 55,000 mPa · s or less,
Each of them is to selectively mix components having a molecular weight of 400 or less and a proportion of less than 7% by weight. However, the tackifier resin and the liquid hydrocarbon having a melt viscosity at 100 ° C. of 55,000 mPa · s or less have a molecular weight of Is 400 or less is 7
Since some of them may exceed 10% by weight, the type and amount of these tackifying resins and liquid hydrocarbons having a melt viscosity at 100 ° C. of 55,000 mPa · s or less are appropriately selected so that the molecular weight is 400 or less in the combination of both. The component may be less than 7% by weight.

In the hot melt adhesive of the present invention, various additives such as inorganic fillers such as calcium carbonate, zinc white, talc, silica, etc., and colorants, etc. may be added, if necessary, without impairing the intended features of the present invention. It is also possible to add within the range. Furthermore, antioxidants may be added, preferably within the range of 3% relative to the total composition.

The hot-melt adhesive of the present invention is used in a melting tank called a heat-melting stirring tank. Method of dissolving in order,
For the production of hot melt adhesives, such as a method of applying a shear under heating with a twin rotary blade called a kneader and a method of melting and mixing under heating with an extruder, that is, a single-screw or twin-screw screw. It can be produced by any method used. Examples of the method of applying the hot melt adhesive to the automobile interior material include a method using a spiral spray, an atomizing spray, a roll coater, or the like. Therefore, the hot melt adhesive needs to have a melt viscosity suitable for these coating methods. Specifically, 100 to 30,000 in the case of spiral spray or atomized spray.
mPa · s, preferably 500 to 20,000 mPa · s
Is. When it is lower than 100 mPa · s, scattering occurs during coating, and when it is higher than 30,000 mPa · s,
It is difficult to secure a sufficient amount of coating. Further, the melt viscosity in the case of roll coater coating is 100 to 50,000 mPa · s, preferably 500 to 20,000 mPa · s. 10
When it is lower than 0 mPa · s, sagging occurs, and 50,
If it is higher than 000, a sufficient coating amount cannot be secured.

INDUSTRIAL APPLICABILITY The present invention can be applied to automobile interior materials in general, for example, soundproof material for dash panel (sound absorbing / insulating material), floor member (bead portion, tunnel portion), trim component (door panel, pillar), parcel shelf, It can be applied to ceiling materials and interior materials for trunk rooms. INDUSTRIAL APPLICABILITY The hot melt adhesive of the present invention is effective for adhesion of high-density felt and low-density felt, adhesion of felt and skin, felt and non-woven fabric, felt and rubber sheet, felt and foamed plastic, and the like.

[0015]

EXAMPLES The present invention will be specifically described below by showing Examples and Comparative Examples, but the present invention is not limited to the following Examples. The parts and% in the examples mean parts by weight and% by weight, respectively.

Example 1 10 parts of styrene-isoprene-styrene block copolymer (manufactured by Nippon Zeon Co., Ltd., trade name: Quintac 3433N, styrene content 16%), hydrogenated aliphatic petroleum resin (Maruzen as a tackifying resin) Petrochemical Co., Ltd., trade name: Marukalets H505, softening point 105 ° C., molecular weight less than 400 component ratio of 75%, 75 parts, liquid polyisoprene rubber as liquid hydrocarbon (Kuraray Co., Ltd., trade name: Klaprene L
IR-30, molecular weight 29,000, melt viscosity at 100 ° C., 35,000 mPa · s, molecular weight less than 400, component ratio 0%, 15 parts, and antioxidant (polymeric hindered polyvalent phenol, Ciba Geigy) 1 part by trade name: Irganox 1010) was melt mixed at 180 ° C. to prepare a hot melt adhesive.

Examples 2 to 8 and Comparative Examples 1 to 8 In the same manner as in Example 1, the respective components were melt-mixed at 180 ° C. based on the composition of the raw material type and the charging amount shown in Table 1, and hot melted. An adhesive was prepared.

[0018]

[Table 1]

Septon 2063: Hydrogenated product of styrene-isoprene-styrene block copolymer, manufactured by Kuraray Co., Ltd., styrene content 13% UT-2535: amorphous polyolefin resin, manufactured by Ube Industries, Ltd., propylene / ethylene type Quinton K-100: Aliphatic petroleum resin, manufactured by Nippon Zeon Co., softening point 101 ° C., molecular weight less than 400 component ratio 7.
5% Alcon P-100: Hydrogenated aromatic petroleum resin, manufactured by Arakawa Chemical Co., Ltd., softening point 100 ° C., molecular weight less than 400 component ratio 26.8% Clearon P105: hydrogenated terpene resin, Yasuhara Chemical Co., softening point 105 C, molecular weight less than 400 Component ratio 24.4% Claprene LIR-200: Liquid polyisoprene rubber (complete hydrogenation type), Kuraray Co., molecular weight 25.0
00, molecular weight less than 400, component ratio 0%, melt viscosity 50,
100 mPa · s (at: 100 ° C.) Process oil PW-32: Paraffin type process oil, manufactured by Idemitsu Kosan Co., Ltd., pour point −17.5 ° C., molecular weight 40
Less than 0 component ratio 40.2%, melt viscosity 1 mPa · s (a
(t: 100 ° C)

Performance tests were conducted on the hot melt adhesives obtained in Examples 1 to 8 and Comparative Examples 1 to 8 with respect to melt viscosity, haze value (fogging property), coating property, and adhesive property. Is shown in Table 2. The test method is as follows. 1. Melt Viscosity The melt viscosity of each hot melt adhesive was measured by a B-type rotational viscometer at a measurement temperature of 180 ° C. according to JIS-K-6862 (Method for testing melt viscosity of hot melt adhesive).
The melt viscosity of the liquid hydrocarbon was measured by the same method as above at a measurement temperature of 100 ° C. 2. Haze value (fogging property) Each hot melt adhesive is applied to an aluminum cup (about 30 in diameter).
(mm × height 20 mm), about 1 g was weighed, the aluminum cup was placed in a glass container, and the mouth of the container was sealed with a glass plate to form a sealed state. Put the glass container containing the sample in a silicone oil bath controlled at a constant temperature (80 ° C.), leave it for 20 hours, then take it out, cool it to room temperature, remove the glass plate, and remove the volatile components adhering to the glass plate. The haze value was measured using a turbidimeter (COH-300A manufactured by Nippon Denshoku Industries Co., Ltd.). 3. Coatability 3-1 and spiral sprayability Each hot melt adhesive was applied using a hand gun for spiral made by Nordson Co., application temperature 180 ° C., application amount 30 to 6
The felt was applied while being adjusted to 0 g / m ² . The state of ejection and breakage of the adhesive when the hand gun was turned on and off, the shape of the spiral, the state of seeping into the felt, etc. were observed, and when all were in good condition, it was indicated by ◯. 3-2 Roll coater coatability Each hot melt adhesive was coated with a roll coater manufactured by Sansei Riko Co., Ltd. at a coating temperature of 180 ° C. and a coating amount of 30 to 60 g /
It was applied to the felt while being adjusted to m ² . After the coating was finished, the adhesive was cut (threading), the state of the coated surface, the state of bleeding into the felt, etc. were observed. 4. Adhesion Felt while preparing each hot melt adhesive at an ambient temperature of 20 ° C. using the above spiral spray gun or roll coater so that the coating temperature is 180 ° C. and the coating amount is 40 g / m ^2. After applying it to the oven time 120
Seconds, pressure of 10 g / cm ² , time of 10 seconds, 200 × 100 m from a sample bonded with another felt of the same type
A test piece of m size was cut out and the following test was conducted. When all were in good condition, it was indicated by ◯. -90 degree bendability The test piece was immediately bent at an angle of 90 degrees, and peeling and floating of the adhesive surface were observed.・ Hanging the heat and cold resistance test piece in a thermostat manufactured by Tabai Espec,
Ten cycles were repeated with one cycle consisting of 8 hours at 20 ° C and 16 hours at 80 ° C. After that, the test piece was returned to room temperature, and peeling and floating of the adhesive surface were observed.

[0021]

[Table 2]

[0022]

INDUSTRIAL APPLICABILITY The hot melt adhesive of the present invention is characterized in that it can be coated with a spiral spray or a roll coater and that it has a small amount of volatile low molecular weight components due to the fogging phenomenon. Therefore, it is possible to provide a hot-melt adhesive that is optimal for adhering an interior material that is mounted on an automobile, and also has an effect of reducing odor in the vehicle interior.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Shintaro Hara             8-16-15 Toyoshima, Kita-ku, Tokyo Japan Special             Paint Co., Ltd. Development Center (72) Inventor Yoshihiro Kitahata             2-17-33 Kitafu, Takefu City, Fukui Prefecture             Gaku Kogyo Co., Ltd. F-term (reference) 4J040 BA202 DA001 DM011 DN031                       DN071 JB01 JB09 LA08                       MA10 MA12 MB02 NA15

Claims (2)

[Claims] 1. (A) Styrene-isoprene-styrene block copolymer, styrene-butadiene-styrene block copolymer, hydrogenated product of styrene-isoprene-styrene block copolymer and / or styrene-butadiene-styrene block. Copolymer hydrogenated product 100
(B) 50 to 800 parts by weight of tackifying resin, and (C) 55,000 mPa · s in melt viscosity at 100 ° C.
The following liquid hydrocarbons are mixed in an amount of 50 to 300 parts by weight, and the ratio of components having a molecular weight of 400 or less in the total composition (A), (B) and (C) is less than 7% by weight. Hot melt adhesive for automobile interior materials. 2. A (D) hydrogenated product of a polyolefin resin or a polyolefin resin and a styrene-isoprene-styrene block copolymer and / or a hydrogenated product of a styrene-butadiene-styrene block copolymer 100
(B) 50 to 800 parts by weight of tackifying resin, and (C) 55,000 mPa · s in melt viscosity at 100 ° C.
The following liquid hydrocarbons are compounded in an amount of 0 to 100 parts by weight, and the ratio of the components having a molecular weight of 400 or less in the total composition (D), (B) and (C) is less than 7% by weight. Hot melt adhesive for automobile interior materials.