JP4414251B2 - Non-slip hot melt composition - Google Patents

Description

  The present invention relates to hot melt compositions. More specifically, the present invention relates to a hot melt composition used for anti-slip processing such as mats, carpets, clothing, and anti-slip tape, and an anti-slip processed product using the same.

Conventionally, various compositions for imparting various properties such as heat resistance, flexibility, plasticizer retention, durability, etc., in addition to anti-slip performance, have been studied for resins for anti-slip processing. Such compositions include soft PVC (polyvinyl chloride), latex, SBR (styrene-butadiene rubber), EVA (ethylene-vinyl acetate copolymer), APAO (non-crystalline polyolefin), styrene block copolymer rubber. A system and a mixture thereof are known (for example, Patent Document 1).
Japanese Patent Laid-Open No. 2001-19926

  However, among these, soft PVC is excellent in durability, flexibility, and moldability, but has low heat resistance, and further, since PVC contains chlorine, it may cause dioxins during incineration in recent years. Use is avoided. Latex is excellent in final performance, but requires a drying step, resulting in problems such as poor productivity and workability and odor. In addition, EVA, APAO, styrene block copolymer rubber, and the like are used as hot melt systems having excellent processability. However, EVA systems are inferior in flexibility and have a problem of low anti-slip effect. The APAO system is superior in flexibility to EVA and has a higher anti-slip effect, but has a problem of weak adhesion to an adherend having a high polarity such as polyester and falling off during use. Further, the conventional styrene block rubber system is excellent in anti-slip property, durability, but heat resistance is not sufficient. That is, the present invention provides a hot melt composition having an excellent balance of anti-slip properties, workability, heat resistance and plasticizer retention, and excellent adhesion to a wide range of substrates from olefins to nylon resins. The purpose is to do.

The present inventors solved these problems, and as a result of intensive studies to obtain a hot melt composition excellent in anti-slip properties, processability, substrate adhesion and heat resistance, and good plasticizer retention, The present invention has been reached.
That is, the present invention provides hardness at 23 ° C. is 5 to 70, a softening point of 100 to 160 ° C., and Ri melt viscosity of 1 to 100 Pa · s der at 180 ° C., diene (co) polymer and One or more rubbers (A) selected from ethylene-α-olefin copolymers, a tackifying resin (B) containing a resin having an aniline point of 30 ° C. or lower, a softening point improver (C), and plastic a and Rubberized products of fibers or resin coating the present composition; agent (D) Tona for Rubberized characterized Rukoto hot melt composition.

The hot melt composition of the present invention has the following effects when applied to mats, carpets and the like as compared with conventional ones.
(1) Excellent balance of anti-slip property, workability and substrate adhesion.
(2) Since the resin is excellent in heat resistance, it is difficult for the resin to cohesively break even in a high temperature atmosphere.
(3) Since plasticizer retention is good, there is little migration of the plasticizer to the coated substrate and the non-contact body.

  The hot melt composition of the present invention has a hardness of 5 to 70, a softening point of 100 to 160 ° C., and a melt viscosity at 180 ° C. (hereinafter referred to as 180 ° C. melt viscosity) of 1 to 100 Pa · s. is there. Only when it is within these ranges can a hot melt composition with a good balance of adhesion, anti-slip properties and processability be obtained.

The hardness at 23 ° C. of the hot melt composition of the present invention is usually 5 to 70, and the lower limit of the hardness is preferably 10, more preferably 15. The upper limit of the hardness is preferably 65, more preferably 60. If the hardness is less than 5, the cohesive force of the hot melt composition is reduced, so that there is a tendency to paste, and if it exceeds 70, the anti-slip effect is reduced, and the texture of the processed product processed with the hot melt composition And tend to be less flexible.
The hardness at 23 ° C. is measured by a spring type hardness test (A type) of JIS K6301-1995.
Hardness test measurement conditions: The pressure surface is pressed vertically with a load of 9.81 N, and the scale after 5 seconds is read.

The softening point of the hot melt composition of the present invention is usually from 100 to 160 ° C., and the lower limit of the softening point (° C.) is preferably 105, more preferably 110. The upper limit is preferably 155, more preferably 150. If the softening point is less than 100, the cohesive force of the hot melt composition tends to decrease, and if it exceeds 160, the melt viscosity tends to increase and the coatability tends to decrease.
The softening point is measured by the ring and ball method according to JIS K6863.

The 180 ° C. melt viscosity of the hot melt composition of the present invention is usually from 1 to 100 Pa · s, and the lower limit of the 180 ° C. melt viscosity (Pa · s) is preferably 1.2, more preferably 1.5. The upper limit is preferably 90, more preferably 80. When the 180 ° C. melt viscosity is less than 1 Pa · s, the cohesive force of the hot melt composition tends to be lowered, and when it exceeds 100 Pa · s, the coatability tends to be lowered.
The 180 ° C. melt viscosity is measured by the following method.
Measurement method: A sample of about 8 g is put into a test tube having an inner diameter of 16 mm and a height of 105 mm, and the temperature is adjusted to 180 ° C. for 20 minutes in an oil bath, and an SB type viscometer (JIS K7117-1987, SB4 spindle, for example, A BL type viscometer manufactured by Toki Sangyo Co., Ltd. and a No. 4 rotor) were set and the temperature was adjusted for another 10 minutes.

  The above numerical range of the hot melt composition of the present invention can be achieved by blending two or more kinds of rubbers, resins, additives, etc., but the kind and amount of the blend are not particularly limited. As an aspect which can achieve the said numerical range, the hot-melt composition which consists of rubber | gum, a softening point improver, and a plasticizer is mentioned, for example. The hardness can be adjusted mainly by rubber, the softening point mainly depends on the softening point of the rubber, but can also be adjusted by a softening point improver, and the melt viscosity can be adjusted mainly by a plasticizer.

  As a preferred embodiment of the present invention, at least one rubber (A) selected from a diene (co) polymer and an ethylene-α-olefin copolymer, a tackifier resin (B), a softening point improver (C) and A hot melt composition comprising the plasticizer (D) is exemplified.

The rubber (A) is at least one rubber selected from a diene (co) polymer and an ethylene-α-olefin copolymer. The number average molecular weight of the rubber (A) is preferably 10,000 to 3,000,000, more preferably 20,000 to 2,000,000, and particularly preferably 30,000 to 1,000,000.
The diene (co) polymer includes a monomer having 4 to 18 carbon atoms (eg, butadiene, isoprene, etc.) or another monomer (diene to other monomer weight ratio of 0.1). (Co) polymer having a structural unit of ˜100: 0 to 99.9) and a hydrogenated product thereof. Other monomers include aromatic vinyl monomers having 8 to 20 carbon atoms (such as styrene), olefins having 2 to 8 carbon atoms (such as ethylene and propylene), and unsaturated nitriles having 3 to 20 carbon atoms. (For example, acrylonitrile etc.) etc. are mentioned.

  Specific examples of the diene (co) polymer include butadiene rubber, isoprene rubber, natural rubber, butyl rubber, nitrile rubber, styrene-butadiene-styrene block copolymer rubber (SBS), styrene-isoprene-styrene block copolymer rubber ( SIS), Styrene-Isoprene-Butadiene-Styrene Block Copolymer Rubber (SIBS), Styrene-Butadiene Random Copolymer Rubber (SBR), Diene (Co) Polymeric Hydrogenation in which Part or All of the Diene Part is Hydrogenated [Styrene- (ethylene-propylene) -styrene block copolymer rubber (SEPS; hydrogenated product of SIS), styrene- (ethylene-butene) -styrene block copolymer rubber (SEBS; hydrogenated product of SBS), styrene- Ethylene- (ethylene-propylene) -styrene block The copolymer rubber (SEEPS; hydrogen embodying the SIBS), hydrogenated SBR, etc.] and the like.

Specific examples of the ethylene-α-olefin copolymer include ethylene and an α-olefin having 3 to 18 carbon atoms (for example, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, etc.) (ethylene and α A copolymer rubber with an olefin weight ratio of 0.1 to 95: 5 to 99.9), ethylene, an α-olefin, and a non-conjugated diene having 4 to 18 carbon atoms (for example, ethylidene norbornene, dicyclopentadiene, etc.) And a terpolymer rubber (weight ratio of ethylene, α-olefin, and nonconjugated diene of 30 to 90: 5 to 80: 0.1 to 30).
Among these, a diene (co) polymer and a hydrogenated product thereof are preferable, SBS, SIS, SEPS, and SEBS are more preferable, and SEEPS excellent in heat resistance and plasticizer retention is particularly preferable. .

As (B), a known plasticizer {adhesion technique 20, (2), 13 (2000), etc.} can be used. For example, rosin having a number average molecular weight (hereinafter referred to as Mn) of 200 to 1,000, Rosin derivative resins (for example, polymerized rosin, rosin ester, etc.), terpene resins having Mn of 300 to 1,300 [for example, (co) polymers such as α-pinene, β-pinene, limonene, and phenol-modified products thereof. ], Coumarone-indene resin, petroleum resin of Mn 300 to 1,200 [for example, (co) polymers such as C5 fraction, C9 fraction, C5 / C9 fraction, dicyclopentadiene], Mn of 200 to 1, Styrene resin having a glass transition temperature (hereinafter referred to as Tg) of 40 ° C. or higher [for example, (co) polymers such as styrene, α-methylstyrene, vinyltoluene, etc.], xylene system having Mn of 300 to 3,000 Examples thereof include one or more resins selected from resins (for example, xylene formaldehyde resins), phenolic resins having Mn of 300 to 3,000 (for example, phenol xylene formaldehyde resins) and hydrogenated products of these resins. Among these, preferred are those having an aniline point of 60 ° C. or lower, more preferred are those having an aniline point of 50 ° C. or lower, and from the viewpoint of improving adhesion to polar substrates (polyester, nylon, etc.). A rosin derivative resin having a Mn of 200 to 1,000, a terpene resin, and a hydrogenated product thereof, and particularly preferred are a phenol-modified product of the terpene resin and a hydrogenated product thereof.
The Mn and the weight average molecular weight (hereinafter referred to as Mw) described above or below are values determined by gel permeation chromatography (GPC) using polystyrene as a standard.

  (C) is not particularly limited as long as it has a softening point or a glass transition point (Tg) determined by a differential scanning calorimetry (DSC) method of 80 to 180 ° C., for example, paraffin wax, microcrystalline wax, Mn1, Low molecular weight polyethylene having a softening point of 100 to 135 ° C. at 000 to 10,000, low molecular weight polypropylene having a softening point of 135 to 160 ° C. at Mn 2,000 to 30,000, and these (anhydrous) unsaturated carboxylic acid graft modified products Low molecular weight polystyrene with a Mn of 1,000 to 10,000 and a softening point of 90 to 160 ° C., low molecular weight polyphenylene oxide (PPO) with a Mn of 1,000 to 10,000 and a Tg of 140 to 180 ° C., and a mixture of two or more thereof. Is mentioned. Of these, low molecular weight polyethylene, low molecular weight polypropylene and their (anhydrous) unsaturated carboxylic acid graft modified products are preferred from the viewpoint of excellent thermal stability and weather resistance, and an effect of improving heat resistance, and particularly preferably Low molecular weight polypropylene.

  As (D), a known plasticizer {adhesion technique 20, (2), 21 (2000), etc.] can be used, for example, paraffinic, naphthenic or aromatic process oil; liquid polybutene, liquid Examples include liquid rubbers having an Mw of 300 to 10,000 such as polybutadiene and liquid polyisoprene; hydrogenated bodies of these liquid rubbers. Among these, paraffinic process oil, naphthenic process oil, and combinations thereof are preferable from the viewpoint of obtaining a composition excellent in thermal stability and weather resistance.

The content (weight) of (A) relative to the total weight of the above (A), (B), (C) and (D) is the content of (A) from the viewpoint of cohesive strength, melt viscosity and plasticizer retention ( The lower limit of (% by weight) is preferably 5, more preferably 8, and particularly preferably 10. The upper limit is preferably 50, more preferably 45, and particularly preferably 40.
The content of (B) is, based on the total weight of (A) to (D), from the viewpoint of substrate adhesion, and the lower limit is preferably 1, more preferably 2, and particularly preferably 3. . The upper limit is preferably 30, more preferably 25, and particularly preferably 20.
From the viewpoint of heat resistance, cohesive strength and melt viscosity, the lower limit of the content of (C) is preferably 1, more preferably 2, particularly preferably based on the total weight of (A) to (D). Is 3. The upper limit is preferably 40, more preferably 35, and particularly preferably 30.
The content of (D) is preferably 25, more preferably 30, and particularly preferably 35 based on the total weight of (A) to (D) from the viewpoint of cohesive strength and melt viscosity. is there. The upper limit is preferably 80, more preferably 75, and particularly preferably 70.

  In the composition of the present invention, the hardness can be mainly adjusted by the rubber (A). When the content of (A) is increased, the hardness tends to decrease. The substrate adhesion can be mainly adjusted by the tackifier resin (B). Alternatively, increasing the content of (B) or lowering the aniline point tends to improve the substrate adhesion. The heat resistance can be mainly adjusted by the softening point improver (C). When the content of (C) or Tg is increased, the heat resistance tends to be improved. The plasticizer (D) can mainly adjust the hardness and melt viscosity. When the content of (D) is increased, the hardness and melt viscosity tend to decrease.

  The hot melt composition of the present invention can contain other additives (E) as necessary. (E) includes an antioxidant {hindered phenol-based compound [for example, pentaerythryl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- ( 3,5-di-t-butyl-4-hydroxyphenyl) propionate, etc.], phosphorus compounds [eg, tris (2,4-di-t-butylphenyl) phosphite, etc.], sulfur compounds [eg, penta Erystil-tetrakis (3-laurylthiopropionate), dilauryl-3,3′-thiodipropionate, etc.], etc.]; UV absorber {benzotriazole-based compound [eg, 2- (3,5-di-) t-amyl-2-hydroxyphenyl) benzotriazole, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, etc. Etc.}; light stabilizer {hindered amine compound [e.g., (bis-2,2,6,6-tetramethyl-4-piperidyl) sebacate, etc.]}; adsorbent (e.g., alumina, silica gel, molecular sieve, etc.); Organic or inorganic fillers (for example, talc, mica, calcium carbonate, etc., titanium oxide, calcium oxide, etc.); pigments; dyes;

When (E) is added, the amount of these additives is preferably 0.01 to 5% by weight of the antioxidant, ultraviolet absorber and light stabilizer, based on the weight of the hot melt composition. Preferably it is 0.1 to 3 weight%.
Moreover, in an adsorbent and a filler, 0.01 to 40 weight% is preferable, More preferably, it is 0.1 to 15 weight%.
Moreover, in a pigment, dye, and a fragrance | flavor, 0.005 to 2 weight% is preferable, More preferably, it is 0.01 to 1 weight%.

Although it does not specifically limit as a manufacturing method of the hot-melt composition of this invention, For example, (i) The method of heat-melt-mixing (A), (B), (C), (D); (ii) Organic solvent (toluene) , Xylene, etc.) and the components are heated and dissolved, and after uniform mixing, the solvent is distilled off. Industrially preferred is the method (i).
Moreover, a heating melt kneader can be used as the mixing device. There are no particular limitations on the form of the heat-melt kneader, but for example, a pressure reactor with a stirrer, a mixer having a highly compressible screw or ribbon stirrer, a kneader, a uniaxial Or a multi-screw extruder, a mixer, etc. can be mentioned. The mixing temperature is usually 80 to 200 ° C., and it is preferably performed in an inert gas atmosphere such as nitrogen gas in order to prevent resin deterioration.

Examples of a method of applying the hot melt composition of the present invention to an adherend include, for example, (i) a method of melting and coating the adherend, and (ii) a film of the hot melt composition between the adherends. The method of melting after interposing is mentioned. Examples of (i) include, but are not limited to, methods such as spiral coating, roll coating, slot coating, control seam coating, and bead coating. Preferably 0.1 to 500 g / m ² in terms coating as coating amount, more preferably from 1 to 300 g / m ² (i.e., 0.1 g / m ² or more, more preferably 1 g / m ² or more, and preferably 500 g / m ² or less, more preferably 300 g / m ² or less.) In wire coating, 0.005 to 100 g / m is preferable, and more preferably 0.01 to 50 g / m ( That is, it is preferably 0.005 g / m or more, more preferably 0.01 g / m or more, and preferably 100 g / m or less, more preferably 50 g / m or less. The thickness of the film (ii) is preferably 1 to 1000 μm, more preferably 5 to 500 μm (that is, preferably 1 μm or more, more preferably 5 μm or more, and preferably 1000 μm or less, more preferably 500 μm or less).
The melting temperature when applied to the adherend is preferably 120 to 220 ° C., and the melt viscosity is preferably 0.5 to 500 Pa · s, more preferably 1 to 100 Pa · s (that is, 0.5 Pa · s or more). More preferably 1 Pa · s or more, 500 Pa · s or less, more preferably 100 Pa · s or less.

  Since the hot melt composition of the present invention is excellent in substrate adhesion, heat resistance, cohesion, flexibility and processability, a wide range of adherends [for example, synthetic fibers (polyester, nylon, acrylics), cotton, silk , Rubber, various plastic molded products, paper, metal, wood, glass, mortar concrete, etc.], especially fibers (polyester, nylon, acrylic, cotton, silk, hemp, hair, etc.), various plastic molded products, etc. Suitable for non-slip processing.

Examples 1-6 and Comparative Examples 1-3
The mixture of each component mixed with the formulation (parts by weight) shown in Table 1 was put into a stainless steel pressure reactor, and the inside of the container was purged with nitrogen. Then, the temperature was raised to 160 ° C. in a sealed state and stirred for 4 hours. The hot melt composition of the present invention and a comparative hot melt composition were obtained.

<Explanation of symbols>
A-1: SEEPS “Septon 4033” (Kuraray)
A-2: SEBS “Clayton G-1657” (manufactured by Kraton Polymer Japan)
B-1: Terpene phenol resin “YS Polystar N-125” (manufactured by Yashara Chemical Co., Ltd .; aniline point = 30 ° C. or less)
B-2: Hydrogenated petroleum resin “Escollets E-5320” (manufactured by Tonex; aniline point = 80 ° C.)
C-1: Low molecular weight polypropylene wax “Biscol 660P” (manufactured by Sanyo Chemical Industries; softening point = 145 ° C.)
C-2: Polyphenylene oxide “Noryl PPO SA120” (manufactured by GE Plastics, Inc .; Tg = 160 ° C.)
D-1: Paraffinic oil “Diana Process Oil PW-90” (manufactured by Idemitsu Kosan Co., Ltd.)
E-1: Hindered phenolic antioxidant “Irganox 1010” (manufactured by Ciba Specialty Chemicals)
E-2: Phosphorous antioxidant “ADK STAB 2112” (manufactured by Asahi Denka Kogyo Co., Ltd.)

Performance test example About each hot-melt-adhesive composition obtained in Examples 1-6 and Comparative Examples 1-3, antiskid property, base-material adhesiveness, heat resistance, and plasticizer retention property were evaluated with the following test method. did. The results are shown in Table 2.
As is clear from Table 2, the hot melt composition of the present invention has a better balance with substrate adhesion, heat resistance, plasticizer retention, and anti-slip performance than those of the comparative examples. I understand.

Evaluation methods
(i) Anti-slip property A sample for evaluation of anti-slip property was applied to a polypropylene non-woven fabric (50 μm thick) with a hot melt composition at 190 ° C. using a roll coater so that the basis weight was 50 g / m ^2. It was.
The anti-slip performance was evaluated by measuring the coefficient of static friction according to JIS P8147. As a test method, a horizontal method was used, and an evaluation sample having a size of 10 cm × 6 cm was measured with a weight of 1 kg, a moving speed of 10 mm / min, and a static friction force measured at room temperature using a glass plate as a horizontal plate. The greater the static friction coefficient, the better the anti-slip performance.
(ii) Substrate adhesion (T-type peel strength)
Each hot melt composition is applied in a bead shape to a PET film of 100 mm x 25 mm x 50 µm thickness as a base material with a width of 25 mm (coating temperature 180 ° C, coating amount 0.06 g / m), and PET films of the same size are laminated together A test sample was obtained. After leaving this sample in a 23 ° C. atmosphere for 24 hours, the peel strength was measured at a tensile speed of 300 mm / min using a tensile tester [Autograph AGS-500B (manufactured by Shimadzu Corporation)], and the maximum value was T The mold peel strength was used (unit: N / 25 mm).

(iii) Heat resistance A hot melt composition sheet was pressed at 180 ° C. using a pressure press molding machine to prepare a hot melt composition sheet sample having a thickness of 1 mm. The obtained sample was cut into 5 cm × 2 cm, sandwiched between 10 cm × 2.5 cm × 1 mm thick stainless steel plate and stored at 100 ° C. for 3 hours with a load of 500 g from the top. It peeled off from the stainless steel plate and the state of the interface was observed visually. The hot melt composition peeled off at the stainless steel plate interface was accepted, and the hot melt composition cohesively broken and remained on the stainless steel plate was rejected.
(iv) Plasticizer retention A sheet sample prepared in the same manner as in the heat resistance evaluation was cut into 10 cm × 5 cm, placed on a P tile (vinyl chloride sheet), and stored at 80 ° C. for 5 days with a 500 g load applied. Later, it was evaluated by visually observing whether or not the plasticizer in the hot melt composition was transferred from the sample to the P tile.
Those in which the plasticizer in the hot melt composition was not recognized to have transferred to the P tile were accepted, and those in which the plasticizer migration was recognized were rejected.

Examples of the non-slip processed product of coated fiber or resin to which the hot melt composition of the present invention is applied include kitchen mats, bath mats, carpets, clothing, and anti-slip tapes. It is not something that can be done.

Claims (4)

Hardness at 23 ° C. is 5 to 70, a softening point is 100 to 160 ° C., and the melt viscosity at 180 ° C. Ri 1 to 100 Pa · s der, diene (co) polymers and ethylene -α- olefin From one or more rubbers (A) selected from a copolymer, a tackifying resin (B) containing a resin having an aniline point of 30 ° C. or lower, a softening point improver (C), and a plasticizer (D) Rubberized for hot-melt composition according to claim such Rukoto. 1 type or 2 types from which said (A) is chosen from a styrene-butadiene-styrene block copolymer, a styrene-isoprene-styrene block copolymer, a styrene-isoprene-butadiene-styrene block copolymer, and these hydrogenated products The hot melt composition according to claim 1, which is as described above. The hot melt composition according to claim 1 or 2, wherein the softening point or glass transition point (Tg) of (C) is 80 to 180 ° C. A non-slip processed product of fiber or resin coated with the hot melt composition according to any one of claims 1 to 3.