JP2019044067A - Hot melt composition - Google Patents

Abstract

To provide a hot melt composition excellent in heat resistance, capable of conducting an application operation by spray easily since it has extremely low viscosity at a high temperature region, and capable of controlling flowability since it has extremely high viscosity in a middle temperature region.SOLUTION: There is provided a hot melt composition containing non-crystalline polyalphaolefin having melt viscosity at 190°C of 100,000 to 300,000 mPa s (A), a tackifier (B), a wax (C), and a sorbitol-based nucleation agent (D), in which the wax (C) is 20 to 60 wt.% based on whole composition.SELECTED DRAWING: None

Description

  The present invention relates to hot melt compositions.

  Generally, a hot melt composition is a non-solvent, environment-friendly, short-time curable, and very easy-to-handle material, so that it is possible to improve the working environment at the manufacturing site. Therefore, hot melt compositions are widely used in the construction field as well as precision fields such as automobiles and electric machines.

  In the past, the applicant at least contains a styrenic block copolymer, a polyphenylene ether resin or modified polyphenylene ether resin having a heat distortion temperature or a glass transition temperature of 120 ° C. or higher, an amorphous polyolefin, a tackifying resin and an antiaging agent, The hot melt composition characterized in that the melt viscosity at 200 ° C. is 30 Pa · s or less was invented (Patent Document 1). This composition is excellent in adhesion to a polyolefin-based material and adhesiveness, is excellent in heat resistance and heat aging resistance, and is low in melt viscosity at around 200 ° C., so is excellent in coatability and dischargeability. It was excellent in workability.

JP 2007-99795 A

  By the way, in the manufacturing process of members in the automotive field and the electric field, a hot melt composition which does not require drying equipment is preferably used to improve productivity, and in that case, coating can be performed efficiently in a short time. In order to do so, a spray method may be adopted. As a specific example, a hot melt composition melted in a high temperature range (about 200 to 250 ° C.) is applied by spray to a substrate such as a molded metal plate or plastic plate, The process which manufactures various members is mentioned by bonding surface layers, such as a fibrous material, and heat-pressing them at about 100-180 degreeC, making it fully solidify and adhere | attach in a low temperature area | region.

  Generally, in order to improve the coatability by spraying, it is necessary to make the hot melt composition such that the viscosity at the coating temperature is as low as possible. However, when a hot melt composition having low viscosity and high fluidity is used in the above process, it once penetrates into the inside of the fibrous material and then leaks, causing appearance defects and physical defect. There was a problem that. There is also a method of setting an open time for a long time in order to suppress leakage after infiltration, but drastic measures have been required because it causes deterioration of productivity.

  The problem to be solved by the present invention is that it is excellent in heat resistance, and in the high temperature region, it can be easily applied by spraying because it has a very low viscosity, and in the middle temperature region it is very high. It is an object of the present invention to provide a hot melt composition whose flowability can be controlled because of its viscosity.

  The present invention provides a noncrystalline polyalphaolefin (A) having a melt viscosity of 100,000 to 300,000 mPa · s at 190 ° C., a tackifier (B), a wax (C), and a sorbitol nucleation core. A hot melt composition comprising an agent (D) and the wax (C) in an amount of 20 to 60% by weight based on the whole composition.

  The hot melt composition according to the present invention is excellent in heat resistance, and in a high temperature region, it can be easily applied by spraying since it has a very low viscosity, and in a medium temperature region, it is very high. Since the viscosity is obtained, there is an effect that the flowability can be controlled.

<Non-crystalline poly alpha olefin>
In the present invention, non-crystalline polyalphaolefin (A) is used. Hereinafter, the said (A) component may be described with "APAO." The component (A) is used as a base polymer of the hot melt composition according to the present invention.

  The melt viscosity of the component (A) at 190 ° C. needs to be in the range of 100,000 to 300,000 mPa · s. The lower limit is preferably 100,000 mPa · s, more preferably 105,000 mPa · s or more, and particularly preferably 110,000 mPa · s or more. The upper limit thereof is preferably less than 300,000 mPa · s, more preferably 250,000 mPa · s or less, and particularly preferably 200,000 mPa · s or less.

  Here, when the melt viscosity at 190 ° C. of the component (A) is less than 100,000 mPa · s, since the viscosity in the medium temperature region is relatively low, it tends to be difficult to control the fluidity . On the other hand, when the melt viscosity at 190 ° C. is more than 300,000 mPa · s, since the viscosity in a high temperature region is relatively high, application by spray tends to be difficult.

  Moreover, as a weight average molecular weight of the said (A) component, the range of 100,000-300,000 can be mentioned. The lower limit thereof is preferably more than 100,000, more preferably 101,000 or more, and particularly preferably 102,000 or more. The upper limit thereof is preferably less than 300,000, more preferably 250,000 or less, and particularly preferably 200,000 or less.

  Here, when the weight average molecular weight of the said (A) component is in said range, there exists a tendency which can be compatible in heat resistance and fluidity.

  In addition, as a compounding ratio of the said (A) component, it is preferable to mix | blend 30-70 weight% with respect to the whole composition, it is still more preferable to mix 35-65 weight%, and 40 to 60 weight% is mix | blended Is particularly preferred.

  As the kind of the component (A), in addition to homopolymers such as polypropylene and polybutene-1 which are non-crystalline polymers, copolymers of propylene and a monomer selected from ethylene, 1-butene and 1-hexene Or terpolymers and the like.

  Specific examples of the component (A) include VESTOPLAST 792 (product name, manufactured by Evonik, melt viscosity (190 ° C.): 120,000 mPa · s, weight average molecular weight (Mw): 118,000), VESTOPLAST 888 (product , Evonik Co., melt viscosity (190 ° C.): 120,000 mPa · s, weight average molecular weight (Mw): 104,000), and the like.

<Tackifier>
In the present invention, a tackifier (B) is used. As a softening point of the said (B) component, the range of 60-200 degreeC can be mentioned. The lower limit thereof is preferably higher than 60 ° C., more preferably 80 ° C. or higher, and particularly preferably 100 ° C. or higher. The upper limit thereof is preferably less than 200 ° C., more preferably 180 ° C. or less, and particularly preferably 160 ° C. or less

  In addition, as a compounding ratio of the said (B) component, it is preferable to mix | blend 1-30 weight% with respect to the whole composition, mix | blending 2-29 weight% is still more preferable, and 3-28 weight% is mix | blended Is particularly preferred.

  Here, when the softening point of the component (B) and the compounding ratio thereof are within the above range, the wettability of the surface of the adherend becomes high, and therefore the adhesion between the layers can be remarkably improved. Tend.

  Examples of the type of the component (B) include terpene resins, terpene phenol resins, aliphatic petroleum resins, aromatic petroleum resins, alicyclic petroleum resins, rosin resins, and modified products thereof.

  Specific examples of the component (B) include T-REZ HA 085 (product name, manufactured by JXTG Energy, softening point: 88 ° C., hydrogenated aromatic petroleum resin), T-REZ HA 125 (product name, manufactured by JXTG Energy, Inc.) Softening point: 125 ° C., hydrogenated aromatic petroleum resin), YS resin PX1250 (product name, manufactured by Yasuhara Chemical Co., Ltd., softening point: 125 ° C., terpene resin), YS polystar U130 (product name, manufactured by Yasuhara Chemical Co., Ltd., softening point: 130 ° C, terpene phenol resin), YS polystar T160 (product name, made by Yashara Chemical Co., softening point: 160 ° C, terpene phenol resin), Picco A120 (product name, made by Eastman Chemical Co., softening point: 125 ° C, aromatic Petroleum resin) and the like.

<Wax>
In the present invention, wax (C) is used. As a melting point of the said (C) component, the range of 80-200 degreeC can be mentioned. The lower limit thereof is preferably 80 ° C., more preferably 100 ° C. or more, and particularly preferably 120 ° C. or more. The upper limit thereof is preferably less than 200 ° C., more preferably 190 ° C. or less, and particularly preferably 180 ° C. or less.

  Here, when the melting point of the component (C) is less than 80 ° C., the viscosity in each temperature range is reduced, which tends to make it difficult to control the fluidity. On the other hand, if the melting point exceeds 200 ° C., it will not melt unless the temperature is raised to an extreme temperature range, so it tends to be unsuitable for use in a normal production process.

  In addition, as a compounding ratio of the said (C) component, it is necessary to mix | blend 20-60 weight% with respect to the whole composition, it is still more preferable to mix 22 to 55 weight%, and it mix | blends 24 to 50 weight% Is particularly preferred.

  Here, when the compounding ratio of the said (C) component is less than 20 weight%, since it does not fully function as a lubricant, there exists a tendency to be inferior to the applicability by spray. On the other hand, when the blending ratio exceeds 60% by weight, although it is excellent in lubricity, it tends to be difficult to control the flowability.

  As a kind of the said (C) component, polyethylene wax, a polypropylene wax, etc. are mentioned as crystalline synthetic wax. Among these, it is preferable to use polypropylene wax.

  Specific examples of the component (C) include Hi-Wax NP 500 (product name, manufactured by Mitsui Chemicals, melting point: 161 ° C., polypropylene wax), H-501 (product name, manufactured by QINGDAO SINOPLAS, melting point: 160 ° C., polypropylene Wax, H-503 (product name, manufactured by QINGDAO SINOPLAS, melting point: 150 ° C., polypropylene wax).

<Sorbitol-type nucleating agent>
In the present invention, a sorbitol-based nucleating agent (D) is used. Generally, types of nucleating agents include sorbitol type, rosin type, naphthalene type, phosphate type and the like, and among these, it is necessary to use a sorbitol type.

  Heretofore, it is known that the component (D) remarkably improves the transparency by blending it with an olefin resin. By blending the component (D) with the above-mentioned components (A) to (C), the inventors of the present application have a very low viscosity in the high temperature region, but very high in the medium temperature region. It was found that the viscosity was high. Although the details of the reaction mechanism are unknown, it is believed that the use of a sorbitol-based nucleating agent only contributes to the formation of a fine crystal structure of the composition according to the present invention.

  In addition, as a mixture ratio of the said (D) component, it is preferable to mix 0.01 to 10 weight% with respect to the whole composition, and it is still more preferable to mix 0.05 to 7 weight%, 0.1 It is particularly preferable to blend at 5 wt%.

  Specific examples of the component (D) include Gelol D (product name, manufactured by Shin Nippon Rika Co., Ltd.), Gel All MD (product name, manufactured by Shin Nippon Rika Co., Ltd.), Millad 3988 (product name, manufactured by Milliken Co., Ltd.) .

  Furthermore, in the present invention, an antiaging agent can be used. Types of the components include phosphites, naphthylamines, p-phenylenediamines, quinolines, hydroquinones, bis-tris-polyphenols, thiobisphenols, hindered phenols, etc. Or it can use combining 2 or more types. Among these, hindered phenols are preferably used. As a specific example of the said component, Songnox 1010 (a product name, the product made by SORDWON company, a hindered phenol type), etc. are mentioned. The blending ratio of the component is preferably 0.01 to 10% by weight, more preferably 0.05 to 7% by weight, and further preferably 0.1 to 5% by weight based on the whole composition. It is particularly preferred to When the kind of the said component and its compounding ratio are in said range, deterioration by a heat | fever can be suppressed efficiently.

  In the hot melt composition according to the present invention, although other components such as fillers such as calcium carbonate, talc and clay, and various additives such as an antioxidant, a preservative and a plasticizer are contained. good.

<Example and Comparative Example>
In the formulations shown in Tables 1 and 2, the mixture was sufficiently kneaded at 220 ° C. in a twin screw extruder to obtain hot melt compositions of Examples and Comparative Examples. Here, the numerical values in Tables 1 and 2 represent parts by weight. The following shows the raw materials used.
APAO: VESTOPLAST 888 (product name, manufactured by Evonik, melt viscosity (190 ° C.): 120,000 mPa · s)
Tackifier: T-REZ HA 125 (product name, manufactured by JXTG Energy, softening point: 125 ° C., hydrogenated aromatic petroleum resin)
Wax: H-501 (product name, manufactured by QINGDAO SINOPLAS, melting point: 160 ° C., polypropylene wax)
Nucleator 1: Gelol D (product name, Shin Nippon Rika Co., Ltd., sorbitol, melting point: 230 ° C.)
Nucleator 2: Pine Crystal KR 50 M (product name, manufactured by Arakawa Chemical Industries, Rosin, melting point: 150 ° C.)
Nucleating agent 3: Adekastab NA11 (product name, manufactured by Adeka, phosphate type, melting point: 410 ° C.)
Nucleating agent 4: Adekastab NA27 (product name, manufactured by Adeka, phosphate type, melting point: 230 ° C.)
Nucleating agent 5: ENJESTER NU 100 (Product name, Shin Nippon Rika Co., Ltd., naphthalene type, melting point: 380 ° C.)
Anti-aging agent: Songnox 1010 (product name, manufactured by SONDWON, hindered phenol type)

  The following physical property evaluation was performed about the hot-melt composition obtained by said Example etc. The results are shown in Tables 3 and 4.

<Softening point>
The softening point (° C.) was measured based on JIS K 6863 using a ring and ball type softening point measurement device (manufactured by Meitec Co., Ltd.).

Melt viscosity
13 ml of the hot melt composition was placed in a cell heated to 160 ° C. or 200 ° C. with a Brookfield BH type viscosity clock, and after 10 minutes, No. Twenty-nine spindles were inserted, and the spindles were rotated at 10 rpm, and the value after 10 minutes was measured to obtain the melt viscosity (cP · s) of the temperature.

<Applicability>
150 g of the hot melt composition was charged into a hot melt gun set at 200 ° C., and was completely melted by maintaining for 1 hour. Then, spray coating was performed on a metal plate (10 cm × 10 cm × 1 mmt) so that the coating amount was 100 g / m ^2, and the appearance after application was visually observed. The case where uniform coating was able to be applied to the whole metal plate was evaluated as 、, and the case where the spray droplets were not stabilized and the coating unevenness occurred on a part of the metal plate was evaluated as x.

<Appearance after bonding>
150 g of the hot melt composition was charged into a hot melt gun set at 200 ° C., and was completely melted by maintaining for 1 hour. Then, spray coating is performed on a metal plate (4 cm × 4 cm × 1 mmt) so that the coating amount is 240 g / m ^2, and 0.21 g / cm ³ non-woven fabric (4 cm × 4 cm × 1 mmt) is applied thereon. It piled up and, at the same time, it was left to stand in a thermostat controlled at 180 ° C., and at the same time, a 500 g metal weight (4 cm × 4 cm × 4 cmt) thermostated in the thermostat was mounted. After leaving as it was for 1 minute, it was taken out from the thermostat, and the surface of the non-woven fabric was visually observed. The case where the exudation due to the leakage of the hot melt composition did not occur on the surface of the non-woven fabric was evaluated as ○, and the case where the exudation occurred was evaluated as x.

  The hot melt compositions according to the examples had extremely good spray coatability, and the appearance after bonding was also extremely excellent. On the other hand, the hot melt composition according to the comparative example was inferior in any of the evaluation items.

Claims (4)

  Amorphous polyalphaolefin (A) having a melt viscosity of 100,000 to 300,000 mPa · s at 190 ° C., a tackifier (B), a wax (C), and a sorbitol nucleating agent (D) And a wax (C) in an amount of 20 to 60% by weight based on the total weight of the composition.   A coating method comprising melting the hot melt composition according to claim 1 at 200 to 250 ° C and applying it by spraying.   A bonding method comprising: bonding a surface layer to a substrate coated by the coating method according to claim 2 at 100 to 180 ° C. and hot pressing.   A method of manufacturing a member manufactured by the bonding method according to claim 3.