TW202134356A - Moisture-curable hot melt composition for electrical/electronic components, bonding agent, and coating agent - Google Patents

Abstract

The present invention provides a moisture-curable hot melt composition for electrical/electronic components, which has a short curing time following application, is excellent in terms of tack-free properties, and exhibits excellent high temperature flow resistance and insulation reliability. Specifically, the present invention provides a moisture-curable hot melt composition for electrical/electronic components, which contains a silyl group-containing amorphous polyolefin (A1), a liquid softening agent (B1) and a catalyst (C). The melt viscosity of the hot melt composition at 120 DEG C is 5000 mPa·s or less. The difference between the storage elastic modulus G' (Pa) and the loss elastic modulus G'' (Pa) at 160 DEG C, as measured using a dynamic viscoelasticity measurement apparatus in rotating shear mode at a vibrational frequency 1 Hz and a temperature increase rate of 5 DEG C/minute within the temperature range -80 DEG C to 200 DEG C, of a cured product obtained by curing the hot melt composition for 72 hours at a temperature of 25 DEG C and a relative humidity of 50% is 1500 Pa or more.

Description

Moisture hardening hot melt composition, potting agent and coating agent for electrical and electronic parts

The invention relates to a moisture-curable hot-melt composition, potting agent and coating agent for electrical and electronic parts.

In the past, electronic components such as IC chips and chip coils were mounted on the surface of electronic circuit packaging substrates. Electronic circuit package substrates such as electronic control unit (ECU) of automobiles, electrical parts of household appliances, sensor parts, etc. are mounted in the housing. In order to protect the metal exposed part of the electronic circuit package substrate from moisture, dust, corrosive gas, etc., it is moisture-proof by potting agent (also called casting compound or sealant) or coating agent Insulation treatment.

Nowadays, two-component polyurethane resins are mostly used as potting agents. Two-component polyurethane resin refers to a polyurethane resin that is used after mixing a main agent mainly composed of polyol components and a hardener mainly composed of isocyanate components. In addition, as the coating agent, a moisture-curing coating agent, an ultraviolet-curing coating agent, a solvent-drying coating agent, etc. are mainly used.

In recent years, the production volume of electronic parts has been increasing. From the viewpoint of productivity, potting agents and coating agents with a short curing time are required. Furthermore, when a coating agent is used for the ECU of an automobile, since it is exposed to a high temperature environment, a coating agent composed of a thermosetting resin is required.

In recent years, in order to improve the productivity of electrical and electronic parts, it has been proposed to replace the two-component polyurethane resin with a one-component sealant for electronic equipment.

As a one-component sealant for electronic devices, Patent Document 1 describes a moisture-curable urethane hot-melt resin composition containing a urethane prepolymer.

Patent Document 2 describes a hot-melt composition containing a modified thermoplastic polymer having an alkoxysilyl group in the molecule, a softener, and a catalyst.

Patent Document 3 describes a coating material which is a coating material for an electronic circuit board and is made of polyolefin resin as a base material and containing 10 to 35 wt% of a softening material.

Patent Document 4 describes a moisture-curable hot-melt resin composition containing: an olefin resin having a moisture-curable silicon group and an aromatic modified terpene resin having a hydroxyl value of 50 mgKOH/g or more. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] JP 2016-108510 [Patent Document 2] International Publication No. 2017/098889 [Patent Document 3] JP 2005-194392 A [Patent Document 4] Japanese Patent Application Publication No. 2011-219569

[The problem to be solved by the invention]

As a one-component moisture-curing sealant, silicone resin is used, but the curing time depends on humidity, etc. Therefore, it sometimes takes several hours to harden to a non-adhesive state, and there is a problem that it affects the productivity of parts.

As the ultraviolet curable coating agent, a coating agent containing acrylic compounds such as urethane acrylate and (meth)acrylate monomers is used. The coating agent will harden immediately after ultraviolet ray irradiation, but depending on the electronic parts, a non-irradiated part may be shielded, and uncured may occur in the non-irradiated part. In particular, the lead part of the IC chip is prone to be unhardened, and there is a problem of reduced insulation reliability.

As a solvent-drying coating agent, a coating agent containing ethylcyclohexane, methylcyclohexane, etc. as a solvent is used. The coating agent has the following problems: the solvent needs to evaporate through a drying step, and it takes time to reach a non-sticky state, and it may take more than 1 hour of drying time at room temperature.

The base polymer of the moisture-curing urethane hot-melt resin composition described in Patent Document 1 has a polyester skeleton, and therefore hydrolysis occurs in a high-temperature and high-humidity environment, and there is a problem that insulation reliability is reduced.

The hot melt composition described in Patent Document 2 is too high in melt viscosity, so it cannot be cast at an appropriate temperature that does not exceed the heat-resistant temperature of the housing resin on which the electronic component is mounted. In order to reduce the melt viscosity, the temperature exceeds 150°C. In the case of melting and casting in the high temperature range, the quality of the mounted electronic parts may be affected, so there is a problem that it cannot be used as a potting agent and coating agent for electronic parts.

The coating material described in Patent Document 3 uses polyolefin resin as the base material, so it does not require a long time to harden, but the melt viscosity at 120°C or 130°C is extremely high, and it has been applied to high-density packaging substrates in recent years. At this time, there is a problem that the above-mentioned coating cannot be completed within the appropriate coating temperature range that does not affect the electronic parts.

The moisture-curable hot-melt resin composition described in Patent Document 4 has an extremely high melt viscosity at 150°C. When it is applied to a packaged substrate, it cannot be completed within an appropriate coating temperature range that does not affect electronic parts. The problem of coating.

In view of the above situation, the purpose of the present invention is to provide a moisture-curable hot-melt composition for electrical and electronic parts that has a short curing time after coating, excellent tack free, and excellent high-temperature resistance and fluidity and insulation reliability. Things. [Technical means to solve the problem]

In order to achieve the above-mentioned object, the inventors have made repeated efforts to study, and as a result, they have found that the inclusion of silicon-based amorphous polyolefin (A1), liquid softener (B1) and catalyst (C) has specific physical properties. The hot-melt composition can accomplish the above-mentioned problems. The present invention is completed after further research by the inventor.

The present invention provides inventions in the aspects disclosed below. Item 1. A moisture-curable hot-melt composition for electrical and electronic parts, which contains: amorphous polyolefin (A1) with silicon base, liquid softener (B1) and catalyst (C), and The melt viscosity of the above-mentioned hot-melt composition at 120°C is 5000 mPa. s below, For the hardened product obtained by curing the above hot melt composition under the conditions of 25°C and 50%RH for 72 hours, use a dynamic viscoelasticity measuring device, in a rotating shear mode with a vibration frequency of 1 Hz, and a temperature rise of 5°C/min. Speed and temperature range from -80°C to 200°C are measured. The measured difference between the storage modulus G'(Pa) and the loss modulus G'(Pa) at 160°C is more than 1500 Pa. Item 2. The moisture-curable hot-melt composition for electrical and electronic parts as described in Item 1, which further contains an amorphous polyolefin (A2) that does not have a silicon base, The content of the above-mentioned amorphous polyolefin (A2) without a silicon group is 20-50 parts by mass relative to 100 parts by mass of the above-mentioned amorphous polyolefin (A1) having a silicon group. Item 3. The moisture-curable hot melt composition for electrical and electronic parts as described in item 1 or 2, wherein the liquid softener (B1) is selected from paraffin-based processing oils, naphthenic-based processing oils, and aromatic-based processing oils , At least one of the group consisting of liquid paraffin, hydrocarbon-based synthetic oil and liquid polybutene. Item 4. The moisture-curable hot-melt composition for electrical and electronic parts according to any one of items 1 to 3, wherein the catalyst (C) is selected from organotin-based catalysts, titanium compounds, bismuth compounds, and amine compounds At least one of the group consisting of. Item 5. The moisture-curable hot-melt composition for electrical and electronic parts according to any one of items 1 to 4, wherein the content of the liquid softener (B1) is relative to the amount of the silicon-based amorphous polyolefin (A1) ) 100 parts by mass is 30 to 140 parts by mass. Item 6. The moisture-curable hot-melt composition for electric and electronic parts as described in any one of items 1 to 5, wherein the content of the catalyst (C) is relative to the amount of the silicon-based amorphous polyolefin (A1) 100 The parts by mass are 0.01 to 0.5 parts by mass. Item 7. The moisture-curable hot-melt composition for electric and electronic parts as described in any one of items 1 to 6, which further contains a wax selected from paraffin wax, vinyl acetate wax, polyethylene wax, polypropylene wax, and At least one solid softener (B2) from the group consisting of Fisher-Quebsch wax, The content of the solid softener (B2) is 10 to 60 parts by mass relative to 100 parts by mass of the amorphous polyolefin (A1) having a silicon group. Item 8. The moisture-curable hot-melt composition for electrical and electronic parts as described in any one of items 1 to 7, which further contains a natural-derived adhesive agent, a petroleum resin-based adhesive agent, and a petroleum resin-based adhesive agent At least one adhesion imparting agent (D) in the group consisting of the hydride of the agent, The content of the adhesion-imparting agent (D) is 30-100 parts by mass relative to 100 parts by mass of the amorphous polyolefin (A1) having a silicon group. Item 9. The moisture-curable hot-melt composition for electrical and electronic parts as described in any one of items 1 to 8, which further contains at least one selected from the group consisting of monomeric aromatic phosphate esters and aromatic condensed phosphate esters A kind of phosphate (E), The content of the phosphoric acid ester (E) is 10 to 60 parts by mass with respect to 100 parts by mass of the amorphous polyolefin (A1) having a silicon group. Item 10. The moisture-curable hot-melt composition for electric and electronic parts described in any one of items 1 to 9 is used as a coating agent, potting agent, adhesive, or coating agent. Item 11. A moisture-curable hot-melt potting agent for electrical and electronic parts, which contains: silicon-based amorphous polyolefin (A1), liquid softener (B1) and catalyst (C), The melt viscosity of the above hot-melt potting agent at 120°C is 5000 mPa. s below, For the cured product obtained by curing the hot melt potting agent for 72 hours under the conditions of 25°C and 50%RH, a dynamic viscoelasticity measuring device was used in a rotational shear mode with a vibration frequency of 1 Hz and a temperature of 5°C/min. The temperature rise rate and the temperature range of -80℃～200℃ are measured. The measured difference between the storage modulus G'(Pa) and the loss modulus G''(Pa) at 160℃ is more than 1500 Pa. Item 12. A moisture-curable hot-melt coating agent for electrical and electronic parts, which contains: silicon-based amorphous polyolefin (A1), liquid softener (B1) and catalyst (C), The melt viscosity of the hot melt coating agent at 140°C is 3000 mPa. s below, For the hardened product obtained by curing the above hot melt coating agent at 25°C and 50%RH for 72 hours, a dynamic viscoelasticity measuring device was used, in a rotational shear mode with a vibration frequency of 1 Hz, and a temperature of 5°C/min. The temperature rise rate and the temperature range of -80℃～200℃ are measured. The measured difference between the storage modulus G'(Pa) and the loss modulus G''(Pa) at 160℃ is more than 1500 Pa. [Effects of Invention]

The moisture-curable hot-melt composition for electric and electronic parts of the present invention has a short curing time after coating, has excellent non-adhesive properties, and has excellent high temperature resistance fluidity and insulation reliability.

Hereinafter, preferred embodiments of the present invention will be described in detail. The description of the constituent elements described below is based on representative embodiments and specific examples, but the present invention is not limited to such embodiments.

In this manual, the numerical range indicated by using "～" means the range that includes the numerical values described before and after "～" as the lower limit and the upper limit.

In this specification, the lower limit means more than the stated value, and the upper limit means less than the stated value. In this specification, the numerical value described as the lower limit and the numerical value described as the upper limit can be combined arbitrarily to define the numerical range.

1. Moisture-curable hot-melt composition for electrical and electronic parts The moisture-curable hot-melt composition for electrical and electronic parts of the present invention (hereinafter also referred to as "the hot-melt composition of the present invention") contains: having a silicon base The amorphous polyolefin (A1), liquid softener (B1) and catalyst (C) are essential components. The melt viscosity of the hot melt composition of the present invention at 120°C is 5000 mPa. s or less. For the cured product obtained by curing the hot-melt composition of the present invention under the conditions of 25°C and 50%RH for 72 hours, a dynamic viscoelasticity measuring device was used in a rotational shear mode with a vibration frequency of 1 Hz, 5°C/min. Measure the temperature in the temperature range of -80℃～200℃. The difference between the measured storage modulus G'(Pa) and the loss modulus G''(Pa) at 160℃ is more than 1500 Pa . Hereinafter, the storage modulus G'and loss modulus G'at 160℃ measured under this condition will also be referred to as “storage modulus G'at 160℃” and “loss modulus G'at 160℃”. '".

The hot-melt composition of the present invention has the above-mentioned requirements, so that the curing time after coating is short, the non-adhesiveness is excellent, and the high-temperature resistance fluidity and insulation reliability are excellent.

Since the hot-melt composition of the present invention does not add a hardener and is solid at room temperature, it can be preferably used as a liquid potting agent or coating agent that is easy to use. Here, being solid at room temperature means that it is in a solidified state at room temperature. In this specification, normal temperature means, for example, 5°C to 35°C.

The reason why the hot-melt composition of the present invention has moisture hardenability is: the silicon base of the amorphous polyolefin (A1) contained in the hot-melt composition and the moisture present in the air (moisture: H ₂ O) The reaction, after hydrolysis and dehydration condensation, forms a cross-linked structure. In other words, when a large amount of non-silicon-based amorphous polyolefin is used as a component of the hot melt composition, the cross-linked structure cannot be formed by moisture, so the hot melt composition does not have moisture curability.

The hot-melt composition of the present invention is solid at room temperature, so it solidifies in a short time (about 30 minutes) after casting or coating. Therefore, the curing time after coating is shortened, and it can be preferably used for electrical and electronic parts, and the productivity of electrical and electronic parts is improved.

The hot-melt composition of the present invention is solid at room temperature, so the hardening time after casting or coating is short, and the non-adhesiveness is excellent.

Hereinafter, each component contained in the hot melt composition of the present invention will be described.

(Amorphous polyolefin with silicon base (A1)) The hot melt composition of the present invention contains: amorphous polyolefin (A1) having a silicon base. In this specification, the amorphous polyolefin (A1) with a silicon base refers to the amorphous polyolefin (A1) with a hydrolyzable silicon base.

Amorphous polyolefin with hydrolyzable silicon group (A1) is a polymer having an amorphous polyolefin constituting the main chain skeleton and a hydrolyzable silicon group bonded to the amorphous polyolefin constituting the main chain skeleton.

As the monomer component of the polyolefin constituting the main chain skeleton of the amorphous polyolefin (A1) having a hydrolyzable silicon group, for example, ethylene, propylene, 1-butene, isobutene, 4-methyl-1-pentene Ene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and other α-olefins . In this specification, "α-olefin" refers to the general term for olefinic hydrocarbons where the double bond is located at the α position (between the terminal carbon and the next carbon).

Examples of the amorphous polyolefin constituting the main chain skeleton of the amorphous polyolefin (A1) having a hydrolyzable silicon group include: homopolymer of α-olefin; ethylene-propylene copolymer, ethylene-propylene-butene copolymer Copolymers of α-olefins such as ethylene-propylene-isobutylene copolymers; copolymers of α-olefins and ethylene other than ethylene; α-olefins and other monomers copolymerizable with them (such as butadiene, 1,4 -Conjugated and non-conjugated dienes such as hexadiene, 7-methyl-1,6-octadiene, 1,8-nonadiene, 1,9-decadiene, cyclopropene, Cyclobutene, cyclopentene, norbornene, dicyclopentadiene and other cyclic olefins) copolymers.

The amorphous polyolefin constituting the main chain skeleton of the amorphous polyolefin (A1) having a hydrolyzable silicon group is preferably an amorphous poly-α-olefin. Amorphous poly-α-olefin is amorphous or low-crystalline. Amorphous or low crystallinity can be confirmed, for example, by using a differential scanning calorimetry (DSC) to raise the temperature of the sample from a low temperature to a high temperature side (for example, from -80°C) at a heating rate of 10°C/min ℃ to 80 ℃), the shift of the reference line was observed at the glass transition temperature, and thereafter, no exothermic peak accompanied by crystallization was observed.

Examples of monomer components constituting the amorphous poly-α-olefin include the above-mentioned α-olefins. As the α-olefin, an α-olefin having 2 to 20 carbon atoms is preferred, and an α-olefin having 2 to 10 carbon atoms is more preferred. Examples of the amorphous poly-α-olefin include the above-mentioned polymers, and ethylene-propylene copolymers, ethylene-propylene-butene copolymers, and ethylene-propylene-isobutylene copolymers are preferred.

In the amorphous polyolefin (A1) having a hydrolyzable silyl group, examples of the hydrolyzable silyl group include -Si(OR ¹ ) _n (R ² ) _3-n (where R ¹ and R ² are independently It represents a hydrocarbon group having 1 to 20 carbon atoms, and n represents an integer of 1 to 3). R ¹ and R ^{2 are} preferably alkyl groups having 1 to 20 carbon atoms. The hydrolyzable silyl group is preferably an alkoxysilyl group.

Examples of hydrolyzable silyl groups include dialkyl alkoxysilyl groups such as dimethylmethoxysilyl and diethylethoxysilyl; methyldimethoxysilyl and ethyldiethyl Alkyl dialkoxysilyl such as oxysilyl; trialkoxysilyl such as trimethoxysilyl and triethoxysilyl.

When the hydrolyzable silyl group bonded to the main chain skeleton of the amorphous polyolefin (A1) with hydrolyzable silyl group is an alkoxysilyl group, they are respectively bonded to the amorphous olefin Alkoxysilyl and alkoxysilyl are respectively hydrolyzed by moisture in the air. Then, the generation of alcohol is separated and a dehydration condensation reaction occurs, and (-Si-O-Si-) is formed between amorphous polyolefins to form a cross-linked structure.

The melt viscosity of the silicon-based amorphous polyolefin (A1) at 190°C is preferably 1,000 to 10,000 mPa. s, more preferably 1500～7000 mPa. s, particularly preferably 2000～5000 mPa. s. If the melt viscosity at 190°C of the amorphous polyolefin (A1) having a silicon base is within the above range, the melt viscosity at 120°C of the hot-melt composition of the present invention will become low. Therefore, when the hot-melt composition of the present invention is used as a potting agent, its casting moldability is excellent.

The weight average molecular weight (Mw) of the silicon-based amorphous polyolefin (A1) is preferably 10,000 to 200,000, more preferably 30,000 to 100,000. If the Mw of the silicon-based amorphous polyolefin (A1) is within the above range, when the hot-melt composition of the present invention is used as a potting agent, its casting moldability is more excellent.

In this specification, the weight average molecular weight (Mw) of the silicon-based amorphous polyolefin (A1) refers to the measured value obtained by using a gel permeation chromatography measuring device and converting it into standard polystyrene.

As the amorphous polyolefin (A1) having a silicon group, known commercially available products can be widely used, and a silicon group can be bonded (grafted) by reacting an amorphous polyolefin with a silane coupling agent. In addition, two or more of these may be mixed and used. Commercial products include the product name "Vestoplast 206" manufactured by Evonik Degussa, which is a silane-modified amorphous poly-α-olefin (silane-modified APAO).

(Amorphous polyolefin without silicon base (A2)) Regarding the hot melt composition of the present invention, the melt viscosity at 120°C is 5000 mPa. s In terms of the following aspects, it is preferable to contain: an amorphous polyolefin (A1) with a silicon group, and an amorphous polyolefin (A2) without a silicon group.

The content of the non-silicon-based amorphous polyolefin (A2) relative to 100 parts by weight of the silicon-based amorphous polyolefin (A1) is preferably 20-50 parts by mass, more preferably 22.5-45 parts by mass, and more preferably It is 25-40 parts by mass, particularly preferably 30-35 parts by mass. If the content of the non-silicon-based amorphous polyolefin (A2) is within the above range, the storage modulus G'of the hot-melt composition of the present invention at 160°C will not be greatly reduced, and it is easy to maintain high-temperature fluidity.

Amorphous polyolefin without silicon base (A2) is a polymer composed of only the amorphous polyolefin constituting the backbone of the main chain.

As the monomer component of the polyolefin constituting the main chain skeleton of the amorphous polyolefin (A2) without a silicon group, the monomer components described in the item of "Amorphous polyolefin with a silicon group (A1)" above can be cited .

Examples of the amorphous polyolefin constituting the main chain skeleton of the amorphous polyolefin (A2) without a silicon group include the copolymers described in the item of "Amorphous polyolefin with a silicon group (A1)" above.

As the amorphous polyolefin that constitutes the main chain skeleton of the amorphous polyolefin (A2) without a silicon group, the description of the amorphous poly-α-olefin and the item of "Amorphous polyolefin with a silicon group (A1)" above The record is the same.

As the non-silicon-based amorphous polyolefin (A2), well-known commercial products can be widely used. Commercial products include the product name "Vestoplast EP V2103" manufactured by Evonik Degussa and the product name "Vestoplast 708" manufactured by Evonik Degussa.

(Liquid softener (B1)) The hot melt composition of the present invention contains a liquid softener (B1). In this manual, "liquid" refers to a state that shows fluidity at room temperature (5°C to 35°C).

As the liquid softener (B1), for example, paraffin series process oil, naphthenic series process oil, aromatic series process oil, liquid paraffin, hydrocarbon series synthetic oil, liquid polybutene, etc. . These liquid softeners (B1) can be used alone or in combination of two or more. Among these liquid softeners (B1), in terms of excellent self-heating stability, preferred are paraffin-based processing oils, naphthenic-based processing oils, liquid paraffins, hydrocarbon-based synthetic oils, and liquid polybutene. Among these liquid softeners (B1), in terms of more excellent self-heating stability, more preferred are paraffin-based processing oils, naphthenic-based processing oils, and hydrocarbon-based synthetic oils. Among these liquid softeners (B1), in terms of more excellent self-heating stability and further improvement of coating adaptability, paraffin-based processing oils and naphthenic-based processing oils are more preferable. Among these liquid softeners (B1), by using paraffin-based processing oils, the melt viscosity of the hot melt composition of the present invention at 120° C. can be further reduced, and the casting moldability can be further improved.

As the paraffin-based processing oil, well-known commercial products can be widely used. Examples of commercially available products include the product name "PW-32" manufactured by Idemitsu Kosan Co., Ltd., the product name "Diana Fresia S32" manufactured by Idemitsu Kosan Co., Ltd., and the product name "PS-32" manufactured by Idemitsu Kosan Co., Ltd. , The product name "PS-90" manufactured by Idemitsu Kosan Co., Ltd., etc.

As the naphthenic processing oil, well-known commercial products can be widely used. As a commercially available product, for example, the product name "KN-4010" manufactured by PetroChina, the product name "Diana Fresia N28" manufactured by Idemitsu Kosan, and the product name "Nyflex222B" manufactured by Nynas are listed.

As the hydrocarbon-based synthetic oil, well-known commercial products can be used. Examples of commercially available products include the product name "LUCANT HC-10" manufactured by Mitsui Chemicals, and the product name "LUCANT HC-20" manufactured by Mitsui Chemicals.

As the liquid polybutene, well-known commercial products can be widely used. As a commercially available product, for example, the product name "Indopol H-100" manufactured by Ineos Corporation and the like can be cited.

The content of the liquid softener (B1) is preferably 30 to 140 parts by mass, more preferably 35 to 130 parts by mass, and still more preferably 40 to 120 parts by mass relative to 100 parts by mass of the amorphous polyolefin (A1) having a silicon group Parts by mass, particularly preferably 45 to 115 parts by mass. If the content of the liquid softener (B1) is within the above range, the melt viscosity at 120°C of the hot melt composition of the present invention can become a more appropriate viscosity, and the casting moldability and coating properties can be improved. Furthermore, if it is within the above range, the storage modulus G'of the hot-melt composition of the present invention at 160° C. will not be greatly reduced, and it will be easy to maintain high-temperature-resistant fluidity.

(Solid softener (B2)) The hot melt composition of the present invention may further contain a solid softener (B2).

Examples of the solid softener (B2) include mineral waxes such as paraffin wax and microcrystalline wax; polyolefin waxes such as polyethylene wax, polypropylene wax, and Fisher-Quebsch wax; ethylene-acetic acid Vinyl acetate waxes such as vinyl ester copolymer (EVA) waxes. These solid softeners (B2) can be used alone or in combination of two or more. Among the solid softeners (B2), in terms of further enhancing foaming inhibition, paraffin wax, EVA wax, polyethylene wax, polypropylene wax and Fisher-Quebsch wax are preferred. , More preferably paraffin wax and Fisher-Quebsch wax.

The content of the solid softener (B2) is preferably 10-60 parts by mass, more preferably 15-50 parts by mass, and still more preferably 20-45 parts by mass relative to 100 parts by mass of amorphous polyolefin (A1) having a silicon group Parts, particularly preferably 25-40 parts by mass. If the content of the solid softener (B2) is within the above range, the hot-melt composition of the present invention will achieve a more appropriate hardness. Furthermore, if the content of the solid softener (B2) is within the above range, when the hot-melt composition of the present invention is used as a potting agent, the moldability of casting is improved, and the insulation reliability of the structured substrate is improved. Furthermore, if the content of the solid softener (B2) is within the above range, when the hot-melt composition of the present invention is used as a coating agent, the coating properties are improved, and the insulation reliability of the package substrate is improved.

As the paraffin wax, a widely-known commercially available product can be used. As a commercially available product, for example, the product name "64-66C" manufactured by China National Petroleum Corporation can be cited.

As the Fisher-Quebsch wax, well-known commercial products can be widely used. As a commercially available product, for example, the product name "SX105" manufactured by Nippon Seikiwa Co., Ltd. and the like can be cited.

The melting point of the solid softener (B2) is preferably 60°C or higher, more preferably 90°C or higher. When the melting point of the solid softener (B2) is above 60°C, the non-sticking time of the hot-melt composition of the present invention becomes shorter, and the productivity of electrical and electronic parts is further improved.

(Catalyst (C)) The hot melt composition of the present invention contains a catalyst (C).

In the present invention, the catalyst (C) has the effect of promoting the hydrolysis of the silicon group caused by moisture in the air, and preferably promoting the dehydration condensation reaction.

Examples of the catalyst (C) include organotin-based catalysts, titanium compounds, bismuth compounds, and amine compounds. These catalysts (C) can be used alone, or two or more of them can be used in combination. Among these catalysts (C), organotin-based catalysts are preferred.

Examples of the organotin catalyst include alkyl tin ester compounds such as dibutyl tin diacetate, dibutyl tin dilaurate, and dibutyl tin dioctoate.

As the titanium compound, for example, tetraisopropoxy titanium, tetra-n-butoxide titanium, tetrakis (2-ethylhexanol) titanium, dipropoxy bis(acetone) titanium (dipropoxy bis( acetylacetonato) titanium), titanate compounds such as isopropoxytitanium octanediol, and titanium chelate compounds.

Examples of bismuth compounds include organic bismuth carboxylates such as bismuth octoate, bismuth neodecanoate, bismuth naphthenate, and bismuth rosinate.

啉、4,4'-(氧基二(2,1-乙烷二基))雙

啉、1,8-二氮雙環[5.4.0]十一-1-烯、1,4-二氮雙環[2.2.2]辛烷、三乙醇胺、N,N'-二甲基哌

、2,2'-二-(N-

啉基)二乙醚、雙(2,6-二甲基-(N-

啉基)乙基)醚、雙(2-(2,6-二甲基-4-(N-

啉基))乙基)-(2-(4-(N-

啉基))乙基)胺、雙(2-(2,6-二甲基-4-(N-

啉基))乙基)-(2-(2,6-二乙基-4-(N-

啉基))乙基)胺、參(2-(4-(N-

啉基))乙基)胺、參(2-(4-(N-

啉基))丙基)胺、參(2-(4-(N-

啉基))丁基)胺、參(2-(2,6-二甲基-4-(N-

啉基))乙基)胺、參(2-(2,6-二乙基-4-(N-

啉基))乙基)胺、參(2-(2-乙基-4-(N-

啉基))乙基)胺、參(2-(2-乙基-4-(N-

啉基))乙基胺等。Examples of amine compounds include: N-methyl

Morpholine, 4,4'-(oxybis(2,1-ethanediyl))bis

Morpholine, 1,8-diazabicyclo[5.4.0]undec-1-ene, 1,4-diazabicyclo[2.2.2]octane, triethanolamine, N,N'-dimethylpiperidine

, 2,2'-two-(N-

Linyl) diethyl ether, bis(2,6-dimethyl-(N-

Alkyl) ethyl) ether, bis(2-(2,6-dimethyl-4-(N-

(Alkolinyl))ethyl)-(2-(4-(N-

(Alkolinyl))ethyl)amine, bis(2-(2,6-dimethyl-4-(N-

(Alkolinyl)) ethyl)-(2-(2,6-diethyl-4-(N-

(Hydroxy)) ethyl) amine, ginseng (2-(4-(N-

(Hydroxy)) ethyl) amine, ginseng (2-(4-(N-

(Hydroxy)) propyl) amine, ginseng (2-(4-(N-

(Hydroxy))butyl)amine, ginseng (2-(2,6-dimethyl-4-(N-

(Hydroxy)) ethyl) amine, ginseng (2-(2,6-diethyl-4-(N-

(Alkolinyl)) ethyl) amine, ginseng (2-(2-ethyl-4-(N-

(Alkolinyl)) ethyl) amine, ginseng (2-(2-ethyl-4-(N-

Linyl)) ethylamine and the like.

In the present invention, the content of the catalyst (C) relative to 100 parts by mass of the amorphous polyolefin (A1) having a silicon group is preferably 0.01 to 0.5 parts by mass, more preferably 0.04 to 0.4 parts by mass, and still more preferably 0.07 to 0.3 parts by mass, particularly preferably 0.1 to 0.2 parts by mass. If the content of the catalyst (C) is within the above range, the silicon group contained in the amorphous polyolefin (A1) is easy to be hydrolyzed, and the hot-melt composition is easy to form a cross-linked structure, making it suitable for high-temperature-resistant fluidity Hardened object.

As the organotin-based catalyst, well-known commercially available products can be widely used. As a commercially available product, for example, the product name "SXL-1SG" manufactured by Daikyo Chemical Industry Co., Ltd. can be cited.

(Adhesive imparting agent (D)) The hot melt composition of the present invention may contain an adhesion imparting agent (D). By containing the adhesion imparting agent (D), the adhesion between the potting layer or coating layer formed by the hot-melt composition of the present invention and the electronic circuit package substrate is further improved.

As the adhesion-imparting agent (D), for example, natural-derived adhesion-imparting agents, hydrogenated products of natural-derived adhesion-imparting agents, petroleum resin-based adhesion-imparting agents, and hydrogenated products of petroleum resin-based adhesion-imparting agents can be used. These adhesion-imparting agents (D) can be used individually or in combination of 2 or more types.

Examples of natural-derived adhesiveness imparting agents include rosin-based adhesiveness imparting agents, terpene-based adhesiveness imparting agents, and the like.

Examples of rosin-based adhesion-imparting agents include: tall rosin, gum rosin, wood rosin, and other unmodified rosins; polymerized rosin; disproportionated rosin; hydrogenated rosin; maleic acid modification Rosin; Fumaric acid modified rosin, etc. In addition, esterified rosin-based adhesion-imparting agents obtained by esterifying these rosin-based adhesion-imparting agents can be used. Specific examples include: glycerol esters, neopentylerythritol esters, methyl esters, methyl esters, and ethyl esters of rosin-based adhesion-imparting agents. Ester, butyl ester, glycol ester, etc.

Examples of terpene-based adhesion-imparting agents include terpene resins such as α-pinene polymers, β-pinene polymers, and dipentene polymers; terpene phenol resins, styrene-modified terpene resins, and hydrogenated terpenes Modified terpene resins such as olefin resins, etc.

Examples of petroleum resin-based adhesion-imparting agents include petroleum resins such as C5-based petroleum resins, C9-based petroleum resins, C5C9-based petroleum resins, and dicyclopentadiene-based petroleum resins. In addition, hydrogenated petroleum resins (hydrogenated products of petroleum resin-based adhesive imparting agents) obtained by adding hydrogen to these petroleum resins can be cited. Specific examples include: hydrogenated C5 resins, hydrogenated C9 resins, and hydrogenated dicyclopentadiene resins. Resins, hydrogenated C5C9 resins, etc.

The above-mentioned C5 series petroleum resin is a petroleum resin using the C5 fraction of petroleum as a raw material. The above-mentioned C9 series petroleum resin is a petroleum resin that uses the C9 fraction of petroleum as a raw material. In addition, the above-mentioned C5C9-based petroleum resin is a petroleum resin using C5 fraction and C9 fraction of petroleum as raw materials. As a C5 fraction, cyclopentadiene, isoprene, pentane, etc. are mentioned. As a C9 fraction, styrene, vinyl toluene, indene, etc. are mentioned. As the C5 series petroleum resin and the C5C9 series petroleum resin, those containing dicyclopentadiene (DCPD) derived from cyclopentadiene, which is one of the C5 fractions, in the skeleton can be preferably used.

In terms of further improving the adhesion between the potting layer or coating layer formed by the hot melt composition of the present invention and the electronic circuit package substrate, the adhesion imparting agent (D) is preferably a terpene-based adhesion imparting agent And its hydride.

As the terpene-based adhesion-imparting agent, well-known commercial products can be widely used. Examples of commercially available products include terpene resin "YS Resin TO-125" manufactured by Yasuhara Chemicals, "YS POLYSTAR G125" terpene phenol resin manufactured by Yasuhara Chemicals, and "SYLVARES 1095" manufactured by Arizona Chemical Company.

As a hydrogenated petroleum resin (hydrogenated product of a petroleum resin-based adhesive imparting agent) obtained by adding hydrogen to a petroleum resin, well-known commercial products can be widely used. As a commercially available product, for example, the product name "Arkon P-115" manufactured by Arakawa Chemical Industry Co., Ltd. can be cited.

In the present invention, the content of the adhesion imparting agent (D) is preferably 30-100 parts by mass relative to 100 parts by mass of the amorphous polyolefin (A1) having a silicon group, more preferably 35-95 parts by mass, and still more preferably It is 40 to 90 parts by mass, particularly preferably 45 to 85 parts by mass. If the content of the adhesion imparting agent (D) is within the above range, the adhesion between the potting layer or coating layer formed by the hot melt composition of the present invention and the electronic circuit package substrate can be further improved.

(Phosphate (E)) The hot-melt composition of the present invention may contain phosphoric acid ester (E). By containing phosphate (E), flame retardancy can be imparted.

As the phosphoric acid ester (E), for example, monomeric aromatic phosphoric acid ester and aromatic condensed phosphoric acid ester can be used. These phosphoric acid esters (E) can be used individually or in combination of 2 or more types.

Examples of monomeric aromatic phosphates include: triphenyl phosphate, tricresyl phosphate, tris(xylene) phosphate, ginseng phosphate (cumyl) ester, and ginseng phosphate (phenylphenyl) ester. , Trinaphthyl phosphate, cresyl phosphate, diphenyl dimethyl phosphate, diphenyl phosphate (2-ethylhexyl) ester, bis(cumyl) phenyl phosphate, etc.

Examples of aromatic condensed phosphoric acid esters include: trialkyl polyphosphate, resorcinol polyphenyl phosphate, resorcinol poly(bis(2,6-xylyl)) phosphate, and p-benzene Diphenol poly(bis(2,6-xylyl)) phosphate, and condensate such as condensation phosphate of these.

As the aromatic condensed phosphoric acid ester, well-known commercial products can be widely used. As a commercially available product, for example, the product name "PX-200" manufactured by Dahachi Chemical Industry Co., Ltd. can be cited.

The content of phosphate (E) is preferably 10-60 parts by mass, more preferably 15-50 parts by mass, and still more preferably 20-45 parts by mass relative to 100 parts by mass of amorphous polyolefin (A1) having a silicon group , Particularly preferably 25-40 parts by mass. If the content of phosphate (E) is within the above range, the flame retardancy of the hot-melt composition of the present invention can be improved, and the non-adhesiveness can be improved.

(Antioxidant (F)) The hot melt composition of the present invention may contain an antioxidant (F).

As the antioxidant (F), for example, 2,6-di-tert-butyl-4-methylphenol, 3-(4'-hydroxy-3',5'-di-tert-butylphenyl)propane N-octadecyl acid, 2,2'-methylene bis(4-methyl-6-tertiary butylphenol), 2,2'-methylene bis(4-ethyl-6-tertiary Butylphenol), 2,4-bis(octylthiomethyl) o-cresol, acrylic acid-2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl) )-4-methylphenyl ester, acrylic acid-2,4-dithirdpentyl-6-[1-(3,5-dithirdpentyl-2-hydroxyphenyl)ethyl]phenyl ester, acrylic acid -2-[1-(2-hydroxy-3,5-di-tertiary pentyl phenyl)] ester, neopentyl erythritol 4-[3-(3,5-di-tertiary butyl-4-hydroxy phenyl) ) Propionate] and other hindered phenolic antioxidants; dilauryl thiodipropionate, lauryl thiodipropionate stearyl thiodipropionate, neopentyl erythritol 4 (3-lauryl thiopropionate) and other sulfur Antioxidants; Phosphorus antioxidants such as ginseng phosphite (nonylphenyl) ester, ginseng phosphite (2,4-di-tert-butylphenyl) ester, etc. These antioxidants (F) can be used individually or in combination of 2 or more types.

The content of antioxidant (F) is preferably 0.05 to 2.5 parts by mass, more preferably 0.1 to 2 parts by mass, and still more preferably 0.3 to 1.5 parts by mass relative to 100 parts by mass of amorphous polyolefin (A1) having a silicon group , Particularly preferably 0.5 to 1 part by mass. If the content of the antioxidant (F) is within the above range, the thermal stability of the hot-melt composition of the present invention at the time of melting becomes good.

(Other additives) The hot-melt composition of the present invention may contain other additives within a range that does not impair the effects of the present invention. As this other additive, a coloring pigment, a flame retardant, etc. are mentioned.

Examples of color pigments include inorganic pigments such as titanium oxide.

As a flame retardant, inorganic flame retardants, such as a melanin flame retardant and magnesium hydroxide, are mentioned, for example.

In the present invention, the content of the above-mentioned other additives relative to 100 parts by mass of the silicon-based amorphous polyolefin (A1) is preferably 0.1-40 parts by mass, more preferably 0.5-30 parts by mass, and still more preferably 1~ 20 parts by mass, particularly preferably 2-10 parts by mass. If the content of the above-mentioned other additives is within the above-mentioned range, when the hot-melt composition of the present invention is used as a potting agent, the casting moldability can be maintained, and the flame retardancy can be improved. If the content of the above-mentioned other additives is within the above-mentioned range, when the hot-melt composition of the present invention is used as a coating agent, the coating property can be maintained and the flame retardancy can be improved.

The hot melt composition of the present invention preferably contains no solvent. Because it does not contain solvents, there is no need for a drying step after coating, which can further shorten the curing time after coating. As a solvent, toluene, xylene, methylcyclohexane, etc. are mentioned, for example.

The hot-melt composition of the present invention preferably contains: an amorphous polyolefin (A1) having a silicon base, a liquid softener (B1) and a catalyst (C), and does not contain a thermoplastic resin. The hot-melt composition of the present invention more preferably contains: amorphous polyolefin (A1) with silicon base, amorphous polyolefin (A2) without silicon base, liquid softener (B1) and catalyst (C), And does not contain thermoplastic resin.

As said thermoplastic resin, a polystyrene resin, a polyolefin resin, a polyester resin, a polyurethane resin etc. are mentioned, for example.

Examples of the above-mentioned polystyrene resin include homopolymers or copolymers of styrene monomers such as styrene, α-methylstyrene, and chlorostyrene; as styrene monomers and vinyl monomers, Styrenic block copolymers of block copolymers of olefin monomers such as propylene monomers and butene monomers; hydrogenated products of the styrenic block copolymers, etc.

Examples of the styrene-based block copolymer include styrene-based thermoplastic elastomers, and more specifically, styrene-butene-styrene copolymer (SBS), styrene-isoprene-benzene Ethylene copolymer (SIS) and so on.

Examples of hydrogenated products of the above-mentioned styrene-based block copolymers include: styrene-ethylene/butylene-styrene copolymer (SEBS: hydrogenated styrene-based thermoplastic elastomer), styrene-ethylene/propylene-styrene Copolymer (SEPS), styrene-ethylene/ethylene/propylene-styrene copolymer (SEEPS), styrene-ethylene/butylene/styrene-styrene copolymer (SEBSS), styrene-ethylene/propylene/benzene Ethylene-styrene copolymer (SEPSS), etc.

Hereinafter, the physical property values of the hot melt composition of the present invention will be described.

(Physical value of hot melt composition) The melt viscosity of the hot melt composition of the present invention at 120°C is 5000 mPa. s or less, so it can achieve the viscosity suitable for casting by an ejector. By casting in each corner of the housing with electronic parts, the reliability of the electronic parts can be improved. Therefore, the hot melt composition of the present invention The material can be preferably used as a potting agent.

In this specification, "melt viscosity at 120°C" refers to the viscosity of a hot melt composition in a heated and melted state at 120°C. As a method of measuring the melt viscosity at 120°C, for example, heating the hot-melt composition to melt it, and measuring the viscosity in the molten state at 120°C using a Brookfield RVT viscometer (Spindle No. 27) The method of determination.

The upper limit of the melt viscosity of the hot melt composition of the present invention at 120°C is preferably 4800 mPa. s, more preferably 4500 mPa. s, and more preferably 4000 mPa. s, particularly preferably 2800 mPa. s. The lower limit of the melt viscosity of the hot melt composition of the present invention at 120°C is preferably 750 mPa. s, more preferably 1000 mPa. s, more preferably 1200 mPa. s, particularly preferably 1300 mPa. s.

For the cured product obtained by curing the hot-melt composition of the present invention under the conditions of 25°C and 50%RH for 72 hours, a dynamic viscoelasticity measuring device was used in a rotational shear mode with a vibration frequency of 1 Hz, 5°C/min. Measure the temperature in the temperature range of -80℃～200℃. The measured difference between the storage modulus G'(Pa) and the loss modulus G'(Pa) at 160℃ (hereinafter also referred to as The value of "Difference") is 1500 Pa or more. By making the difference between the temperature-storage modulus G'curve and the temperature-loss modulus G'curve measured under the above conditions to be more than 1500 Pa, the high-temperature fluidity of the hot-melt composition of the present invention can be improved , Can be preferably used for electrical and electronic components mounted with electronic circuit package substrates and the like. The upper limit of the above difference is preferably 6000 Pa, more preferably 5000 Pa, and particularly preferably 4500 Pa.

The above difference can be measured by the following method. Specifically, the hot-melt composition of the present invention is heated and melted at 120° C., and flows onto the PET film subjected to the demolding treatment. Next, prepare another PET film subjected to demolding treatment, overlay it on the hot-melt composition so that the demolded surface is in contact with the hot-melt composition, and compress it to a thickness of 1 mm by a hot press. Then, with the above-mentioned hot-melt composition sandwiched between the demolded PET films, it was allowed to stand for 72 hours under the conditions of 25° C. and 50% RH. Then, the release film was removed, and a cured product of the hot-melt composition (hereinafter referred to as "cured product") was produced as a sample for dynamic viscoelasticity measurement. Furthermore, the hardened product of the hot-melt composition is preferably a hardened film of the hot-melt composition.

Assemble the above-mentioned hardened product to a dynamic viscoelasticity measuring device, and perform dynamic viscoelasticity in a rotating shear mode with a vibration frequency of 1 Hz, a temperature range of -80°C to 200°C, and a temperature rise rate of 5°C/min. Determination (heating process). According to the temperature-storage modulus G'curve (horizontal axis: temperature, vertical axis: storage modulus G') and temperature-loss modulus G'' curve (horizontal axis: temperature, vertical axis: loss) obtained by measurement Modulus G''), calculate the storage modulus G'(Pa) at 160°C and the loss modulus G'' (Pa) at 160°C. Then, calculate the difference between the storage modulus G'(Pa) at 160°C and the loss modulus G'' (Pa) at 160°C.

As a dynamic viscoelasticity measuring device, for example, a rotational rheometer manufactured by TA Instruments (trade name "AR-G2") or the like can be used.

The upper limit of the melt viscosity of the hot melt composition of the present invention at 140°C is preferably 3000 mPa. s, more preferably 2400 mPa. s, more preferably 1600 mPa. s, particularly preferably 1100 mPa. s. If the melt viscosity at 140°C is below the upper limit, when the hot-melt composition is coated on the electronic circuit package substrate by an ejector, it will penetrate between the parts on the electronic circuit package substrate to form The smooth and uniform coating surface will improve the reliability of the electronic circuit package substrate, so the hot-melt composition of the present invention can be preferably used as a coating agent.

The lower limit of the melt viscosity of the hot melt composition of the present invention at 140°C is preferably 400 mPa. s, more preferably 500 mPa. s, more preferably 600 mPa. s, 700 mPa is particularly preferred. s.

In this specification, "melt viscosity at 140°C" refers to the viscosity of a hot melt composition in a heated and melted state at 140°C. As a method of measuring the melt viscosity at 140°C, for example, the hot-melt composition is heated and melted, and the viscosity in the molten state at 140°C is measured using a Brookfield RVT viscometer (Spindle No. 27).

2. Manufacturing method and application of moisture-curable hot-melt composition for electrical and electronic parts Manufactured by a well-known method. For example, the above-mentioned amorphous polyolefin with silicon base (A1), liquid softener (B1), catalyst (C), non-silicon base amorphous polyolefin (A2), and adhesion imparting The agent (D), phosphate (E), antioxidant (F) and other additives mentioned above are put into a stirring kneader equipped with a heating device, heated at 120°C for 90 minutes, melted and kneaded, and cooled to solid to produce the present invention The hot melt composition.

3. Uses of the moisture-curable hot-melt composition for electrical and electronic parts As a preferred use of the hot-melt composition of the present invention, coating agents, potting agents, adhesives, coating agents, etc. can be cited. Among them, the hot-melt composition of the present invention is preferably used as a potting agent or coating agent because it has excellent non-adhesion and insulation reliability.

4. Moisture-curable hot-melt potting agent for electrical and electronic parts . A preferred embodiment of the present invention contains: amorphous polyolefin (A1) with silicon base, liquid softener (B1) and catalyst (C ) Moisture-curing hot-melt potting agent for electrical and electronic parts (hereinafter also referred to as "the hot-melt potting agent of the present invention"). The hot melt potting agent of the present invention has a melting viscosity of 5000 mPa at 120°C. s or less. For the cured product obtained by curing the hot-melt potting agent of the present invention under the conditions of 25°C and 50%RH for 72 hours, a dynamic viscoelasticity measuring device is used, and the vibration frequency is 1 Hz in a rotating shear mode, 5°C/ The temperature rise rate in minutes and the temperature range of -80℃～200℃ are measured. The difference between the measured storage modulus G'(Pa) and the loss modulus G'' (Pa) at 160°C is 1500 Pa above.

The hot-melt potting agent of the present invention can be preferably used for electrical and electronic components mounted with electronic circuit package substrates and the like. The hot-melt potting agent of the present invention is solid at room temperature and solidifies immediately after being cast into electrical and electronic parts. Therefore, compared with the two-component potting agent, it has superior non-adhesiveness. Furthermore, the melt viscosity of the hot-melt potting agent of the present invention at 120°C is 5000 mPa. s or less, the castability is excellent, and the cross-linking reaction will be more promoted with time after curing, so the high-temperature fluidity and insulation reliability are excellent.

The components contained in the hot-melt potting agent of the present invention are the same as those described in the item "1. Moisture-curable hot-melt composition for electrical and electronic parts".

As a method of using the hot-melt potting agent of the present invention to seal electrical and electronic components mounted with electronic circuit package substrates, for example, the hot-melt potting agent of the present invention can be melted at a temperature of approximately 120-140°C and sprayed The machine sprays to the surface of the electrical and electronic parts equipped with the electronic circuit package substrate for sealing.

5. Moisture-curable hot-melt coating agent for electrical and electronic parts . Another preferred embodiment of the present invention contains: amorphous polyolefin (A1) with silicon base, liquid softener (B1) and catalyst ( C) Moisture-curable hot-melt coating agent for electrical and electronic parts (hereinafter also referred to as "the hot-melt coating agent of the present invention"). The melt viscosity of the hot melt coating agent of the present invention at 140°C is 3000 mPa. s or less. For the cured product obtained by curing the hot-melt coating agent of the present invention at 25°C and 50%RH for 72 hours, a dynamic viscoelasticity measuring device was used in a rotational shear mode with a vibration frequency of 1 Hz, 5°C/ The temperature rise rate in minutes and the temperature range of -80℃～200℃ are measured. The difference between the measured storage modulus G'(Pa) and the loss modulus G'' (Pa) at 160°C is 1500 Pa above.

The hot melt coating agent of the present invention can be preferably used for electrical and electronic components mounted with electronic circuit package substrates and the like. The hot-melt coating agent of the present invention is solid at room temperature and solidifies immediately after being coated on the circuit package substrate. Therefore, it has superior non-adhesiveness compared with solvent-drying or moisture-curing coating agents. Furthermore, the melt viscosity of the hot melt coating agent of the present invention at 140°C is 3000 mPa. s or less, so it is excellent in coatability, and the crosslinking reaction is more promoted with time after curing, so it is excellent in high temperature resistance fluidity and insulation reliability.

The components contained in the hot-melt coating agent of the present invention are the same as those described in the item "1. Moisture-curable hot-melt composition for electrical and electronic parts".

The upper limit of the melt viscosity of the hot melt coating agent of the present invention at 140°C is preferably 2400 mPa. s, more preferably 1600 mPa. s, particularly preferably 1100 mPa. s. If the melt viscosity at 140°C is below the upper limit, when the hot-melt coating agent is applied on the electronic circuit package substrate by an ejector, it will penetrate between the parts on the electronic circuit package substrate to form The smooth and uniform coating surface can further improve the reliability of the electronic circuit package substrate.

The lower limit of the melt viscosity of the hot melt coating agent of the present invention at 140°C is preferably 400 mPa. s, more preferably 500 mPa. s, more preferably 600 mPa. s, 700 mPa is particularly preferred. s.

As a method of coating an electronic circuit package substrate using the hot melt coating agent of the present invention, for example, the hot melt coating agent of the present invention is melted at a temperature of approximately 140 to 150°C, and the coating device is used to coat the electronic circuit package. Method of coating circuit package substrate. [Example]

Hereinafter, the present invention will be specifically described with examples, but the present invention is not limited to the following examples.

The raw materials used in the examples and comparative examples are as follows.

＜Amorphous polyolefin with silicon base (A1)＞ . (A1-1) Silane-modified amorphous poly-α-olefin (silane-modified APAO): manufactured by Evonik Degussa, Vestoplast 206 (Mw=38000, melt viscosity at 190℃=5000 mPa·s) ＜Amorphous polyolefin without silicon base (A2)＞ . (A2-1) Non-silicon-based amorphous poly-α-olefin: manufactured by Evonik Degussa, Vestoplast EP V2103 (Mw=50,000, melt viscosity at 190℃=2500 mPa·s) . (A2-2) Non-silicon-based amorphous poly-α-olefin: manufactured by Evonik Degussa, Vestoplast 708 (Mw=75000, melt viscosity at 190℃=8000 mPa·s)

＜Liquid softener (B1)＞ . (B1-1) Liquid polybutene: manufactured by Ineos, Indopol H-100 . (B1-2) Naphthenic processing oil: manufactured by China National Petroleum Corporation, KN-4010 . (B1-3) Paraffin-based processing oil: manufactured by Idemitsu Kosan Co., Ltd., PS-90

＜Solid softener (B2)＞ . (B2-1) Paraffin wax: made by China National Petroleum Corporation, Paraffin Wax 64-66C (melting point = 65°C) . (B2-2) Fisher-Quebsch wax: manufactured by Nippon Fine Wax Co., Ltd., SX105 (melting point = 105°C)

＜Catalyst (C)＞ . (C-1) Organotin catalyst: manufactured by Daxie Chemical Industry Co., Ltd., SXL-1SG

＜Adhesion imparting agent (D)＞ . (D-1) Hydrogenated petroleum resin: manufactured by Arakawa Chemical Industry Co., Ltd., Arkon P-115 (softening point 115°C)

＜Phosphate (E)＞ . (E-1) Aromatic condensed phosphoric acid ester: manufactured by Dahachi Chemical Industry Co., Ltd., PX-200

＜Antioxidant (F)＞ . (F-1) Hindered phenol antioxidant: made by BASF, IRGANOX 1010

(Examples and Comparative Examples) The above-mentioned raw materials were put into a stirring kneader equipped with a heating device in the blending amounts shown in Table 1, respectively. It was heated at 120°C for 90 minutes, kneaded, and cooled until it became a solid to produce a hot melt composition.

For the manufactured hot-melt composition, the physical properties were evaluated under the following measurement conditions. Furthermore, "melt viscosity at 120°C" refers to the physical properties obtained when a hot melt composition is used as a potting agent. "Melting viscosity at 140°C" refers to the physical properties obtained when a hot melt composition is used as a coating agent.

(Melting viscosity at 120℃) The hot-melt composition is heated to melt, and the viscosity in the molten state at 120°C is measured using a Brookfield RVT viscometer (Spindle No. 27).

(Melting viscosity at 140℃) The hot-melt composition is heated to melt, and the viscosity in the molten state at 140°C is measured using a Brookfield RVT viscometer (Spindle No. 27).

(Production of samples for dynamic viscoelasticity measurement) In order to determine the storage modulus G'and the loss modulus G'', the samples for dynamic viscoelasticity measurement were prepared in the following order (1) to (4). Furthermore, the following PET film 1 and PET film 2 are the same type of PET film. (1) Heat the hot-melt composition at 120°C to melt it, and make it flow onto the PET film 1 subjected to the demolding treatment. (2) Prepare the PET film 2 subjected to demolding treatment, and overlay the hot-melt composition on the PET film 1 in such a way that the demolded surface of the PET film 2 is in contact with the hot-melt composition on the PET film 1. Compressed by a hot press to a thickness of 1 mm. (3) The hot-melt composition is sandwiched between the demolded PET film 1 and the PET film 2, and it is allowed to stand at 25°C and 50%RH for 72 hours. (4) Remove the PET film 1 and PET film 2 that have been demolded, and obtain a hardened film of the hot-melt composition as a sample for dynamic viscoelasticity measurement.

(Measurement method of storage modulus G'and loss modulus G'' at 160℃) The obtained hardened film was assembled in a dynamic viscoelasticity measuring device (manufactured by TA Instruments, Rotational Rheometer "AR-G2"), in a rotational shear mode with a vibration frequency of 1 Hz, a heating rate of 5°C/min,- The dynamic viscoelasticity is measured under the temperature range of 80℃～200℃. According to the temperature-storage modulus G'curve (horizontal axis: temperature, vertical axis: storage modulus G') and temperature-loss modulus G'' curve (horizontal axis: temperature, vertical axis: loss) obtained by measurement Modulus G'') Calculate the storage modulus G'(Pa) at 160°C and the loss modulus G'' (Pa) at 160°C. Then, calculate the difference between the storage modulus G'(Pa) at 160°C and the loss modulus G'' (Pa) at 160°C.

(Casting formability) Prepare a glass bottle (manufactured by Baiyang Glass Co., Ltd., "M-70", with a capacity of approximately 83 ml), fill it with glass beads (8 mm in diameter) to a distance of 15 mm from the upper end of the glass bottle, and use it as a molded body to be cast. Use coating device (manufactured by Nordson Corporation, applicator (applicator, Unity IC30 PLUS), three-axis robot (w/4XP Robot), Unity controller, 30 ml syringe, nozzle diameter 1.35 mm), at a melting temperature of 120 ℃ , Set the distance between the upper surface of the glass bead as the molded body to be cast and the nozzle of the applicator to 10 mm, and cast the hot-melt composition. The casting moldability of the hot melt composition was evaluated based on the following evaluation criteria. Furthermore, if the evaluation is above △, the hot-melt composition can be used as a potting agent. ○: The hot-melt composition penetrates more than 15 mm from the upper end of the filled glass beads △: The hot-melt composition penetrates more than 10 mm and less than 15 mm from the upper end of the filled glass beads ×: The penetration of the hot-melt composition from the upper end of the filled glass beads is less than 10 mm.

(Non-adhesive) By the same method as the above-mentioned measuring method of casting moldability, after 30 minutes, the surface coated with the hot-melt composition was pressed with a finger, and the non-adhesiveness was evaluated based on the following evaluation criteria. Furthermore, if the evaluation is above △, it is judged that there is no problem in actual use. ○: Not at all sticky △: Slightly sticky, but the hot-melt composition does not adhere to the finger ×: sticky, and the hot-melt composition adheres to the finger

(High temperature resistance fluidity) The hot melt composition heated to 120°C and melted flows onto a 70 cm×150 cm steel plate. Then, the peeled PET film is superimposed on the hot melt composition in such a way that the peeling surface is in contact with the hot melt composition, and is compressed by a hot press to a thickness of 2 mm. Cool to room temperature, cut a straight line incision in the central part of the hot-melt composition to divide it into two areas, and remove the hot-melt composition in one of the areas from the center of the incision to the end face. Sample. The sample was allowed to stand for 72 hours under the conditions of 25° C. and 50% RH to obtain a hardened product (hardened film of a hot-melt composition). The obtained hardened product was vertically erected in an oven heated to 120°C, and allowed to stand for 30 days. After 30 days, the degree of sagging of the hot-melt composition from the cut was measured, and the high-temperature resistance fluidity was evaluated based on the following evaluation criteria. ○: No sagging at all. ×: The amount of sag from the incision exceeds 2 mm

(Insulation reliability) Use coating device (manufactured by Nordson Corporation, applicator (Unity IC30 PLUS), nozzle 1.35 mm, syringe 30 ml, three-axis robot (w/4XP Robot), Unity controller), and the thickness becomes The hot-melt composition is applied to a comb-shaped electrode substrate conforming to "JIS Z 3197 8.5.3e" at a melting temperature of 120°C in a 1 mm method. The coated hot-melt composition is cured for 72 hours under the conditions of 25° C. and 50% RH to obtain a cured product. For the obtained hardened product, use a migration tester at 85°C and 87.5%RH to conduct a 500-hour high-temperature and high-humidity insulation reliability test to determine the insulation resistance (Ω) of the hardened product. ○: The insulation resistance value after the test is 10 ⁸ Ω or more. ×: The insulation resistance value does not reach 10 ⁸ Ω. Or the hardened film of the hot-melt composition flows during the test, and the test cannot be continued.

(Coatability) Use the coating device (manufactured by Nordson Corporation, applicator (Unity IC30 PLUS), nozzle diameter 0.62 mm, syringe 30 ml, three-axis robot (w/4XP Robot), Unity controller) to perform the following programming, that is, The coating speed is set to 50 mm/sec, the distance (distance) between the copper foil laminate and the nozzle tip is set to 3 mm, the copper foil laminate is 8 cm×12 cm as the coating area, and the coating is performed in a bead shape , So as to apply the hot-melt composition to the copper foil laminated board (FR-4 base material, size: 14 cm×9 cm). The coating properties of the hot melt composition were evaluated based on the following evaluation criteria. Furthermore, if it is an evaluation of △ or more, it is evaluated that the hot-melt composition can be used as a coating agent. ◎: The surface of the coating film after coating is uniform and smooth, and no coating streaks are observed. ○: Slight coating streaks can be observed on the surface of the coating film after coating, but the smoothness is maintained. △: Slight coating streaks and slight unevenness can be observed on the surface of the coating film after coating. ×: The surface of the coating film completely loses its smoothness, and significant bead-like coating traces and unevenness of the coating surface can be observed.

[Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Comparative example 1 Composition (parts by mass) Amorphous polyolefin with silicon base (A1) (A1-1) 100 100 100 100 100 100 100 100 100 100 - Amorphous polyolefin without silicon base (A2) (A2-1) - 33 33 33 33 33 33 25 33 33 33 (A2-2) - - - - - - - - - - 100 Liquid softener (B1) (B1-1) 115 115 - 82 82 - - 49 82 - 115 (B1-2) - - 115 - - 82 - - - 48 - (B1-3) - - - - - - 82 - - - - Solid softener (B2) (B2-1) - - - 33 - 33 33 25 33 33 - (B2-2) - - - - 33 - - - - - - Catalyst (C) (C-1) 0.13 0.13 0.13 0.13 0.13 0.13 0.13 0.13 0.13 0.13 0.13 Adhesive imparting agent (D) (D-1) - - - 83 83 83 83 50 83 83 - Phosphate (E) (E-1) - - - - - - - - 33 33 - Antioxidant (F) (F-1) 1 1 1 1 1 1 1 1 1 1 1 Evaluation Melt viscosity of hot melt composition at 120℃ (mPa.s) 4000 4950 2175 2800 3313 1475 1325 4313 2913 2075 5990 Melt viscosity of hot melt composition at 140℃ (mPa.s) 2363 2766 1213 1513 1762 756 673 2235 1471 1022 2550 Storage modulus G'(Pa) at 160℃ 4249 4059 2391 2414 2679 2057 2074 4587 4132 4622 269 Loss modulus G'' (Pa) at 160℃ 470 274 289 353 492 346 393 593 467 282 261 Difference between G'and G'' (Pa) 3779 3785 2102 2061 2187 1711 1681 3994 3665 4340 8 Non-stickiness △ △ △ ○ ○ ○ ○ ○ ○ ○ X High temperature fluidity ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ X Casting formability △ △ ○ ○ △ ○ ○ △ △ ○ X Coatability ○ △ ◎ ◎ ○ ◎ ◎ ○ ◎ ◎ △ Insulation reliability ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ X

According to the results shown in Table 1, the hot-melt compositions obtained in Examples 1 to 10 are evaluated as "○" in terms of non-stickiness, high temperature resistance fluidity, casting formability, coating properties and insulation reliability. Or "△", so it can be used as a hot-melt composition for electronic and electrical parts. In particular, the hot-melt compositions obtained in Examples 4, 6, 7 and 10 are evaluated as "○" in terms of non-stickiness, high temperature resistance fluidity, casting formability and insulation reliability, so they can be used preferably It is used as a potting agent for sealing electrical and electronic components mounted with electronic circuit package substrates and other components. In addition, the hot-melt compositions obtained in Examples 4, 6, 7 and 10 were evaluated as "○" in terms of non-stickiness, high-temperature resistance fluidity, and insulation reliability, and the applicability was evaluated as "◎" Therefore, it can be preferably used as a coating agent for coating circuit package substrates. In contrast, the hot-melt composition obtained in Comparative Example 1 was evaluated as "×" in terms of non-stickiness, high-temperature-resistant fluidity, casting moldability, and insulation reliability, and the applicability was evaluated as "×" , So it is not suitable for electrical and electronic parts equipped with electronic circuit package substrates, etc.

without

without

Claims (12)

A moisture-curable hot-melt composition for electrical and electronic parts, which contains: amorphous polyolefin (A1) with silicon base, liquid softener (B1) and catalyst (C), and The melt viscosity of the above-mentioned hot-melt composition at 120°C is 5000 mPa. s below, For the hardened product obtained by curing the above hot melt composition under the conditions of 25°C and 50%RH for 72 hours, use a dynamic viscoelasticity measuring device, in a rotating shear mode with a vibration frequency of 1 Hz, and a temperature rise of 5°C/min. Speed and temperature range from -80°C to 200°C are measured. The measured difference between the storage modulus G'(Pa) and the loss modulus G'(Pa) at 160°C is more than 1500 Pa. For example, the moisture-curable hot-melt composition for electrical and electronic parts of claim 1, which further contains non-silicon-based amorphous polyolefin (A2), The content of the above-mentioned amorphous polyolefin (A2) without a silicon group is 20-50 parts by mass relative to 100 parts by mass of the above-mentioned amorphous polyolefin (A1) having a silicon group. Such as the moisture-curable hot-melt composition for electrical and electronic parts of claim 1 or 2, wherein the liquid softener (B1) is selected from paraffin-based processing oils, naphthenic-based processing oils, aromatic-based processing oils, At least one of the group consisting of liquid paraffin, hydrocarbon-based synthetic oil, and liquid polybutene. The moisture-curable hot-melt composition for electrical and electronic parts according to any one of claims 1 to 3, wherein the above-mentioned catalyst (C) is selected from organotin-based catalysts, titanium compounds, bismuth compounds and amine compounds At least one of the group consisting of. The moisture-curable hot-melt composition for electrical and electronic parts according to any one of claims 1 to 4, wherein the content of the liquid softener (B1) is relative to the silicon-based amorphous polyolefin (A1) 100 parts by mass is 30 to 140 parts by mass. The moisture-curable hot-melt composition for electrical and electronic parts according to any one of claims 1 to 5, wherein the content of the above-mentioned catalyst (C) is relative to 100 masses of the above-mentioned amorphous polyolefin (A1) having a silicon base The parts are 0.01 to 0.5 parts by mass. Such as the moisture-curable hot-melt composition for electrical and electronic parts of any one of claims 1 to 6, which further contains selected from paraffin waxes, vinyl acetate waxes, polyethylene waxes, polypropylene waxes, and waxes. At least one solid softener (B2) from the group consisting of Snow-Quebsch wax, The content of the solid softener (B2) is 10 to 60 parts by mass relative to 100 parts by mass of the amorphous polyolefin (A1) having a silicon group. The moisture-curable hot-melt composition for electrical and electronic parts according to any one of claims 1 to 7, which further contains a natural-derived adhesive imparting agent, a petroleum resin-based adhesive imparting agent, and a petroleum resin-based adhesive imparting agent At least one adhesion imparting agent (D) in the group consisting of hydrides, The content of the adhesion-imparting agent (D) is 30-100 parts by mass relative to 100 parts by mass of the amorphous polyolefin (A1) having a silicon group. The moisture-curable hot-melt composition for electrical and electronic parts according to any one of claims 1 to 8, which further contains at least one selected from the group consisting of monomeric aromatic phosphate esters and aromatic condensed phosphate esters Phosphate (E), The content of the phosphoric acid ester (E) is 10 to 60 parts by mass with respect to 100 parts by mass of the amorphous polyolefin (A1) having a silicon group. The moisture-curable hot-melt composition for electrical and electronic parts according to any one of claims 1 to 9, which is used as a coating agent, potting agent, adhesive or coating agent. A moisture-curable hot-melt potting agent for electrical and electronic parts, which contains: silicon-based amorphous polyolefin (A1), liquid softener (B1) and catalyst (C), The melt viscosity of the above hot-melt potting agent at 120°C is 5000 mPa. s below, For the cured product obtained by curing the hot melt potting agent for 72 hours under the conditions of 25°C and 50%RH, a dynamic viscoelasticity measuring device was used in a rotational shear mode with a vibration frequency of 1 Hz and a temperature of 5°C/min. The temperature rise rate and the temperature range of -80℃～200℃ are measured. The measured difference between the storage modulus G'(Pa) and the loss modulus G''(Pa) at 160℃ is more than 1500 Pa. A moisture-curable hot-melt coating agent for electrical and electronic parts, which contains: silicon-based amorphous polyolefin (A1), liquid softener (B1) and catalyst (C), The melt viscosity of the hot melt coating agent at 140°C is 3000 mPa. s below, For the hardened product obtained by curing the above hot melt coating agent at 25°C and 50%RH for 72 hours, a dynamic viscoelasticity measuring device was used, in a rotational shear mode with a vibration frequency of 1 Hz, and a temperature of 5°C/min. The temperature rise rate and the temperature range of -80℃～200℃ are measured. The measured difference between the storage modulus G'(Pa) and the loss modulus G''(Pa) at 160℃ is more than 1500 Pa.