WO2020196864A1

WO2020196864A1 - Foam, sound-absorbing material, resin composition, sound-absorbing method, sound-absorbing structure, sound-absorbing structure production method, sound-absorbing material production method, building, and vehicle

Info

Publication number: WO2020196864A1
Application number: PCT/JP2020/014160
Authority: WO
Inventors: 博志神山
Original assignee: 株式会社カネカ
Priority date: 2019-03-27
Filing date: 2020-03-27
Publication date: 2020-10-01

Abstract

Provided are a foam and sound-absorbing material that have excellent sound-absorbing characteristics, and a building and vehicle that comprise said sound-absorbing material. Further provided are a resin composition that is capable of suppressing a decrease in the foaming ratio of foam over time, a foam that is obtained using said resin composition, and a foam production method that uses said resin composition. Further provided are a sound-absorbing material that excellently absorbs sound over a wide frequency band, a sound-absorbing method that uses said sound-absorbing material, a sound-absorbing structure that comprises the sound-absorbing material, and a method for producing said sound-absorbing structure. The foam is produced by foaming and curing a base material resin (A) having a reactive silicon group containing a polyoxyalkylene polymer (A1); or the resin composition, which contains a base material resin (A) having a reactive silicon group, a chemical foaming agent (B) and a silanol condensation catalyst (D), contains a polyoxyalkylene polymer (A1) and an acrylic resin (A2) having a glass transition temperature of 35°C or more; or a foam exhibiting a shear modulus and a flow resistance per unit thickness of specific values is used as the sound-absorbing material.

Description

Foam, sound absorbing material, resin composition, sound absorbing method, sound absorbing structure, manufacturing method of sound absorbing structure, manufacturing method of sound absorbing material, building, and vehicle

The present invention comprises a foam exhibiting good sound absorbing characteristics, a sound absorbing material provided with the foam, a resin composition for giving the foam, a sound absorbing material composed of the foam, and a sound absorbing method using the sound absorbing material. , The sound absorbing structure provided with the above-mentioned sound absorbing material, the vehicle provided with the above-mentioned sound absorbing structure, the method for manufacturing the above-mentioned sound absorbing structure, the method for manufacturing the above-mentioned sound absorbing material, and the building provided with the above-mentioned sound absorbing material. Regarding vehicles.

As a foam of a polymer compound, a foam using a thermoplastic resin such as polystyrene, polyethylene, polypropylene, or polyvinyl chloride is well known. Taking advantage of its sound absorbing characteristics, such foams are used in the fields of civil engineering and construction, packaging, home appliances, automobiles, etc. in the form of beads, sheets, or boards, for example. In particular, such a foam is used as a sound absorbing material in various articles such as buildings such as houses and vehicles (see, for example, Patent Document 1).

In addition, a sound absorbing material that absorbs noise in various frequency bands is required. Then, various sound absorbing materials are used according to the frequency of the sound to be absorbed. The above-mentioned foam using a thermoplastic resin such as polystyrene, polyethylene, polypropylene, or polyvinyl chloride is used as a sound absorbing material for absorbing noise at a relatively high frequency. Asphalt sheets and the like are used to absorb low-frequency noise such as road noise generated by vehicles such as automobiles.

Further, as a foam using a thermosetting resin, a foam using a modified silicone resin is known. Specifically, a base resin (A) which has a silicon group having a hydrolyzable group and whose main chain is a polymer composed of an oxyalkylene-based unit, a silanol condensation catalyst (B), a bicarbonate, etc. A foam obtained by curing a liquid resin composition containing a chemical foaming agent (C) containing the above by heating is known (see Patent Document 2).

Japanese Unexamined Patent Publication No. 2012-189783 International Publication No. 2016/021630

However, the sound absorption performance of a foam made of a resin such as polyurethane is not always sufficient. Therefore, the sound absorbing material used in the sound absorbing method for absorbing noise and the like is required to have improved sound absorbing characteristics.

Further, when a foam is produced using a liquid composition containing a chemical foaming agent described in Patent Document 1 and the like, even if a high foaming ratio can be achieved within a certain period of time from the start of foaming of the chemical foaming agent, the lapse of time thereafter. In many cases, the foaming ratio is lowered.

And, in the frequency band of 2000 Hz or less, the sound absorption performance of the foam made of a resin such as polyurethane is not always sufficient. In particular, there is no known sound absorbing material that exhibits good sound absorbing characteristics in a high frequency band of more than 2000 Hz and a low frequency band of 1000 Hz or less.

As a result of diligent studies on the above problems, the present inventor foams and cures a base resin (A) having a reactive silicon group containing a polyoxyalkylene polymer (A1) to produce a foam. As a result, they have found that it is possible to produce a foam exhibiting good sound absorbing characteristics in a wide frequency range of 1000 Hz to 5500 Hz, and have completed the present invention.

Further, the present inventor has added a poly as a base resin (A) to a resin composition containing a base resin (A) having a reactive silicon group, a chemical foaming agent (B), and a silanol condensation catalyst (D). It has been found that by containing an oxyalkylene polymer (A1) and an acrylic resin (A2) having a glass transition temperature of 35 ° C. or higher, it is possible to suppress a decrease in the foaming ratio over time when producing a foam. , The present invention has been completed.

Further, the present inventor uses a foam having a shear modulus of 7,000 Pa or less and a flow resistance of 1,000,000 N · s / m ⁴ or more per unit thickness as a sound absorbing material, even in a high frequency band of more than 2000 Hz. , It has been found that a sound absorbing material showing good sound absorbing characteristics can be provided even in a low frequency band of 1000 Hz or less, and the present invention has been completed.

That is, the present invention has the following configuration.
1) A foam obtained by foaming and curing a base resin (A) having a reactive silicon group containing a polyoxyalkylene polymer (A1).
A foam having a sound absorption coefficient of 70% or more at a frequency of 1000 Hz to 5500 Hz, measured using a B tube at 20 ° C. using a sample having a thickness of 25 mm and in accordance with JIS A 1405-2.
2) Using a sample with a thickness of 25 mm, the sound absorption coefficient measured using the B tube at 20 ° C. in accordance with JIS A 1405-2 shows the maximum in the frequency range of 1000 Hz to 1700 Hz to 1). The foam described.
3) Using a sample with a thickness of 25 mm, the sound absorption coefficient at a frequency of 800 Hz is 40% or more, measured using a B tube at 20 ° C. in accordance with JIS A 1405-2, 1) or 2). The foam described in.
4) A foam obtained by foaming and curing a foam resin composition containing a base resin (A) and a chemical foaming agent (B).
The foam according to any one of 1) to 3), wherein the content of the metal salt and / or inorganic particles in the foam is 2.5% by weight or less based on the weight of the foam.
5) The foam according to 4), wherein the chemical foaming agent (B) is a non-pyrolytic type.
6) The foam according to 5), wherein the chemical foaming agent (B) contains a dicarbonate diester (B-1).
7) The foam according to any one of 1) to 6), wherein the base resin (A) contains an acrylic resin (A2) having a glass transition temperature of 35 ° C. or higher.
8) The reactive silicon group is a trimethoxysilyl group, a (methoxymethyl) dimethoxysilyl group, the following formulas (1) to (3):

(In formulas (1) to (3), R ¹ is an independently hydrocarbon group having 1 or more and 20 or less carbon atoms, and the hydrocarbon group as R ¹ may be substituted. Further, it may have a hetero-containing group, X is a hydroxy group or a hydrolyzable group, a is 1, 2, or 3, and R ⁴ is a divalent linking group, which R ⁴ has. The two bonds are bonded to a carbon atom, an oxygen atom, a nitrogen atom, or a sulfur atom in the linking group, respectively, and R ² and R ³ are independently hydrogen atoms and 1 or more carbon atoms, respectively. It is either an alkyl group having 20 or less, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a silyl group.)
The group represented by and the following formula (4):
-R ^5- CH _2- Si (R ¹ ) _3-a (X) _a (4)
(In the formula (4), R1, and a are the same as ^{R 1,} and a in equation (1) to (3), ^{R 5} is a heteroatom.)
The foam according to any one of 1) to 7), which is a group selected from the group consisting of the groups represented by.
9) The foam according to any one of 1) to 8), which has a foaming ratio of 15 to 60 times.
10) The foam according to any one of 1) to 9), which has an FP hardness of 60 or less at 0 ° C.
11) Contains the base resin (A), the chemical foaming agent (B), and the silanol condensation catalyst (D).
The base resin (A) has a reactive silicon group and has.
The base resin (A) contains a polyoxyalkylene polymer (A1) and an acrylic resin (A2) having a glass transition temperature of 35 ° C. or higher.
A resin that gives a foam having a sound absorption coefficient of 70% or more at frequencies of 1000 Hz to 5500 Hz, measured using a B tube at 20 ° C., in accordance with JIS A 1405-2, using a sample having a thickness of 25 mm. Composition.
12) The resin composition according to 11), wherein the base resin (A) has a branch in the main chain structure and has three or more ends.
13) A sound absorbing material comprising the foam according to any one of 1) to 10).
14) Shear modulus is 7000 Pa or less,
A sound absorbing material made of a foam having a flow resistance of 1000000 N · s / m ⁴ or more per unit thickness.
15) The sound absorbing material according to 14), which has a density of 100 kg / m ³ or less.
16) The sound absorbing material according to 14) or 15), wherein the foam comprises a composition containing a polyoxyalkylene polymer.
17) The sound absorbing material according to 16), wherein the foam is a cured product of a resin composition containing a polyoxyalkylene polymer (A1) having a reactive silicon group.
18) The cured product of a resin composition in which the foam contains a polyoxyalkylene polymer (A1) having a reactive silicon group and an acrylic resin (A2) having a reactive silicon group, 17). Sound absorbing material.
19) The total of the content of the inorganic fine particles of the foam and the content of the metal atom contained in the foam as a metal salt in the foam is 2.5% by weight or less, any of 14) to 18). The sound absorbing material described in one.
20) At a frequency of 650 Hz, a vertical incident sound absorption coefficient of 0.15 or more is measured using an acoustic tube with an inner diameter of 40 mm and a test piece with a thickness of 10 mm in accordance with JIS A1405-2. The sound absorbing material according to any one of 14) to 19), which shows a vertically incident sound absorbing coefficient of 0.4 or more at any frequency within a frequency range of 650 Hz or more and 1000 Hz or less.
21) The vertical incident sound absorption coefficient measured using an acoustic tube with an inner diameter of 40 mm and a test piece with a thickness of 10 mm in accordance with JIS A1405-2 in the frequency range of 1000 Hz or more and 4500 Hz or less is 0.45. The sound absorbing material according to any one of 14) to 20) described above.
22) With respect to the foam, the sound absorption coefficient at a frequency of 1000 Hz to 5500 Hz measured using a B tube at 20 ° C. using a sample having a thickness of 25 mm is 70% or more in accordance with JIS A 1405-2. , 17) or 18).
23) For the foam, the vertical incident transmission loss is 7 dB or more at a frequency of 1000 Hz to 4500 Hz, which is measured using a sample having a thickness of 10 mm and an acoustic tube having an inner diameter of 40 mm according to ASTM E2611.
The sound absorbing material according to any one of 14) to 22), which has sound insulating properties.
24) A sound absorbing method for causing the sound absorbing material according to any one of 14) to 23) to absorb sound containing a component having a frequency in the range of 650 Hz or more and 4500 Hz or less.
25) The sound absorbing method according to 24), wherein the sound to be absorbed contains a component in the frequency range of 650 Hz or more and 1000 Hz or less.
26) A sound insulation method for insulating sound containing components in the frequency range of 1000 Hz to 4500 or less by using the sound absorbing material according to 23).
27) A sound absorbing structure composed of the sound absorbing material according to any one of 14) to 23) and a support supporting the sound absorbing material.
28) The sound absorbing structure according to 27), wherein the support is a pneumatic tire, and the sound absorbing material is supported by the tire so as to cover at least a part of the inner surface of the pneumatic tire.
29) The support consists of a motor and a casing that houses the motor.
27) The sound absorbing structure according to 27), wherein the gap between the motor and the casing is filled with a sound absorbing material.
30) A vehicle comprising the sound absorbing structure according to any one of 27) to 29).
31) A method for manufacturing a sound absorbing structure comprising the sound absorbing material according to any one of 14) to 23) and a support supporting the sound absorbing material.
A method for manufacturing a sound absorbing structure, in which the sound absorbing material is fixed to the surface of a support or the sound absorbing material is filled in a space defined by the support.
32) A liquid resin composition containing a polyoxyalkylene polymer (A1) having a reactive silicon group is applied to the surface of a support or filled in the space defined by the support. When,
By curing the resin composition while foaming it to form a foam, the foam as a sound absorbing material is adhered to the surface of the support.
31). The method for manufacturing a sound absorbing structure.
33) The method for manufacturing a sound absorbing structure according to 32), wherein a liquid resin composition is applied to the surface of the tire as a support on the lumen side.
34) The method for manufacturing a sound absorbing structure according to 32), wherein in a support including a motor and a casing accommodating the motor, a liquid resin composition is filled in a gap between the motor and the casing.
35) Forming a formwork using a 3D printer
Injecting a liquid resin composition containing a polyoxyalkylene polymer (A1) having a reactive silicon group into a mold, and
The method for producing a sound absorbing material according to any one of 14) to 23), wherein the resin composition is cured while being foamed to form a foam.
36) A building provided with the sound absorbing material according to any one of 13) to 23).
37) A vehicle provided with the sound absorbing material according to any one of 13) to 23).

According to the present invention, it is possible to provide a foam having good sound absorbing characteristics in a wide frequency range, a sound absorbing material provided with the foam, and a building and a vehicle provided with the sound absorbing material.
Further, according to the present invention, when a foam is produced using a chemical foaming agent, a resin composition for forming a foam that can suppress a decrease in the foaming ratio over time after the foaming ratio has increased, and the said resin composition. It is possible to provide a foam obtained by foaming and curing a resin composition, and a method for producing a foam using the resin composition.
Further, according to the present invention, a sound absorbing material exhibiting good sound absorbing characteristics in a wide frequency band including a low frequency band of 1000 Hz or less and a high frequency band of more than 2000 Hz, a sound absorbing method using the sound absorbing material, and the above-mentioned sound absorbing material. A sound absorbing structure including the above-mentioned sound absorbing structure, a vehicle provided with the above-mentioned sound absorbing structure, and a method for manufacturing the above-mentioned sound absorbing structure can be provided.

It is a figure which shows the sound absorption coefficient of the foam of Example 3 and the foam of Comparative Example 1. It is a figure which shows the sound absorption coefficient of the foam of Example 2 and the foam of Example 3. It is a figure which shows the vertical incident sound absorption coefficient of the sound absorbing material of Example 8. It is a figure which shows the vertical incident sound absorption coefficient of the sound absorbing material of Example 9. It is a figure which shows the vertical incident sound absorption coefficient of the sound absorbing material of the comparative example 3. It is a figure which shows the vertical incident sound absorption coefficient of the sound absorbing material of the comparative example 4. It is a figure which shows the vertical incident sound absorption coefficient of the sound absorbing material of the comparative example 5. It is a figure which shows the vertical incident sound absorption coefficient of the sound absorbing material of the comparative example 6. It is a figure which shows the vertical incident sound absorption coefficient of the sound absorbing material of the comparative example 7. It is a figure which shows the vertical incident sound absorption coefficient of the sound absorbing material of the comparative example 8. It is a figure which shows the vertical incident sound absorption coefficient of the sound absorbing material of the comparative example 9. It is a figure which shows the vertical incident sound absorption coefficient of the sound absorbing material of the comparative example 10. It is a figure which shows the vertical incident transmission loss of the sound absorbing material of Example 8, Example 9, Comparative Example 3, Comparative Example 4, Comparative Example 8, and Comparative Example 9.

≪ Foam≫
The foam is a foam obtained by foaming and curing a base resin (A) having a reactive silicon group containing a polyoxyalkylene polymer (A1).
With respect to such a foam, the sound absorption coefficient at a frequency of 1000 Hz to 5500 Hz measured using a B tube at 20 ° C. using a sample having a thickness of 25 mm is 70% or more in accordance with JIS A 1405-2.

The foam has a maximum sound absorption coefficient in the frequency range of 1000 Hz to 1700 Hz measured using a B tube at 20 ° C. in accordance with JIS A 1405-2 using a sample having a thickness of 25 mm. preferable.
Further, regarding the foam, the sound absorption coefficient at a frequency of 800 Hz, which is measured by using a sample having a thickness of 25 mm and using a B tube at 20 ° C. in accordance with JIS A 1405-2, is 40% or more. preferable.
Furthermore, the foam has a sound absorption coefficient of 90% or more at a frequency of 1500 Hz, which is measured using a B tube at 20 ° C. using a sample having a thickness of 25 mm and in accordance with JIS A 1405-2. preferable.

The base resin (A), the chemical foaming agent (B), and the silanol condensation catalyst (D) are contained, and as the base resin (A), the polyoxyalkylene polymer (A1) and the glass transition temperature are different. When a foam is formed by using a foam resin composition containing a combination of an acrylic resin (A2) having a temperature of less than 35 ° C., a decrease in the foaming ratio over time is suppressed.
Even when the above foam is produced by the continuous method, it is produced by foaming and curing in a short time while ensuring a sufficient time until the shape of the resin composition for foam becomes a predetermined shape. Therefore, the shape and density are uniform, and a foam having a high foaming ratio can be stably produced.

The foam absorbs well the components in the frequency range of 1000 Hz to 5500 Hz, and particularly well absorbs the components in the frequency range of 1000 Hz to 1700 Hz among the sounds to be absorbed.
Sounds containing components in the frequency range of 1000 Hz to 1700 Hz include daily conversation, musical instrument sounds such as piano and clarinet. Therefore, the above-mentioned foam tends to absorb noise that is particularly annoying in daily life.

Further, when a conventionally known foam is used as a sound absorbing material, the skin layer is often cut off for the purpose of enhancing the sound absorbing characteristics. However, the above foam has a small effect on the sound absorption characteristics with and without the skin layer. For example, when a foam is constructed using a resin composition for a foam at a construction site or a manufacturing site of various products, it may be difficult to cut the skin layer. However, since the above-mentioned foam has a small effect on the sound absorption characteristics of the presence or absence of the skin layer, the sound absorption characteristics of the foam can be sufficiently maintained even if the foam is applied at a construction site or a manufacturing site of various products. It can be demonstrated.
As described above, since the above foam is easily installed at the construction site, it can be easily installed on the inner wall or the gap together with the hard heat insulating material in a building such as a house. As will be described later, the above-mentioned foam has a low FP hardness and is flexible. Therefore, in a building such as a house, if the above foam is applied to the inner wall or the gap together with the hard heat insulating material, the shaking of the earthquake can be absorbed and the hard heat insulating material can be prevented from cracking. As a result, even in the event of an earthquake, it is possible to maintain high heat insulation and airtightness of buildings such as houses.

The use of the above foam is not particularly limited. The above-mentioned foam can be suitably used in applications to which various conventionally known foams such as polyurethane foam and polystyrene foam are applied.

The shape of the foam is not particularly limited. Examples of the shape of the foam include a sheet shape, a rod shape, a regular polyhedron shape (for example, a cube shape, a regular tetrahedron shape, a regular octahedron shape, etc.), a disk shape, a spherical shape, a hemispherical shape, an indefinite shape, and the like. From the viewpoint that it can be preferably produced by the continuous method, the shape of the foam is preferably sheet-like or rod-like. The rod shape is a shape in a stationary state. Since the foam is flexible, the foam may behave like a string when the rod-shaped foam is moved in a stationary state.

The density of the foam is not particularly limited as long as the foam exhibits the desired sound absorbing characteristics. Density of the foam, for example, preferably 200 kg / ^{m 3} or less, more preferably 150 kg / ^{m 3} or less, 100 kg / ^{m 3} more preferably less, still more preferably 50 kg / ^{m 3} or less. When the density is within this range, the sound absorbing characteristics of the foam are good, and the foam is relatively lightweight and easy to carry on a daily basis, so that the foam can be applied to buildings as a sound absorbing material. It's easy. The lower limit of the density of the foam is not particularly limited, but may be 10 kg / m ³ or more, 30 kg / m ³ or more, and 70 kg / m ³ or more. If the density is too low, when the foam is used as a sound absorbing material, it may be easily deformed by its own weight.

The hardness of the foam is not particularly limited. The hardness of the foam is appropriately determined according to the use of the foam and the performance required for the foam. The hardness of the foam is preferably 60 or less, more preferably 50 or less, further preferably 15 or less, still more preferably 10 or less, as the FP hardness (ASKER FP hardness) measured at 0 ° C.

The above foam is suitably used for sound absorbing materials. The sound absorbing material provided with the above foam and its use will be described in detail later.
The use of the foam is not limited to the sound absorbing material. The foam can be suitably used as a soundproofing material, a vibration damping material, a cushioning material, etc., for applications such as transportation equipment, bedding / bedding, furniture, various equipment, building materials, packaging materials, medical / nursing care, and the like.

Preferred applications include seats for automobiles, construction machinery, railroad vehicles, ships, aircraft, etc., child seats, headrests, armrests, footrests, headliners, saddles / rider cushions for motorcycles / bicycles, custom cars, etc. Bed mats, cushioning materials for camper cushions, skin materials, skin lining materials, ceiling materials, handles, door trims, instrument panels, dashboards, door panels, pillars, console boxes, quarter trims, sun visors, flexible containers, front Core materials such as mirrors, harnesses and dust covers, skin and skin lining materials, vibration damping and sound absorbing materials such as floor cushions, helmet linings, crash pads, cushioning materials such as center pillar garnish, energy absorption bumpers, guard soundproofing materials, vehicles Examples include wax sponges.

Examples of bedding / bedding applications include cushioning materials such as pillows, comforters, mattresses, beds, mattresses, bed mats, bed pads, cushions, baby beds, and baby neck pillows, as well as skin materials and skin lining materials.

Examples of furniture applications include various cushions such as chairs, seat chairs, cushions, sofas, sofa cushions and seat cushions, cushion materials such as carpets and mats, kotatsu mats and comforters, and toilet seat mats, and skin materials and skin lining materials. Be done.

Examples of various device applications include sealing / cushioning materials for liquid crystals, electronic parts, robot skin, conductive cushioning materials, antistatic cushioning materials, pressure sensing materials, and the like.

Examples of building material applications include heat insulating materials for floors and roofs, shock absorbers for floors and walls, and the like.
Examples of packaging materials include packaging materials such as cushioning materials, cushioning materials, and shock absorbing materials.
For medical and long-term care applications, cell sheets for regenerative medicine, artificial skin, artificial bones, artificial cartilage, artificial organs, other biocompatible materials, chemical exudation pads, hemostatic pads, gas-liquid separation filters (indwelling needle filters), and adhesives Agents, medical liquid absorbents, masks, compression pads, surgical disposable products, low frequency treatment device electrode pads, bedsore prevention mattresses, repositioning cushions, wheelchair cushions, wheelchair seats, shower chairs and other nursing care products, bathing Also used for nursing care pillows, palm protectors for contraction, taping, cast liners, artificial limbs / legs liners, tooth pads, other dental products, shock absorbing pads, hip protectors, elbow / knee protectors, wound dressings, etc. It can be done.

In addition, for example, the following uses can be mentioned.

Examples of various cleaning sponge applications include cleaning cleaners, dishwashing cleaners, body cleaning cleaners, shoe polish cleaners, car wash cleaners, and the like.
Examples of toiletry applications include absorbent materials such as diapers and sanitary napkins, side gathers, and various liquid filters.

Examples of footwear applications include shoe skin materials, linings, insoles, shoe anti-scratch pads, various shoe pads, inner boots, slippers, slipper cores, sandals, sandal insoles, etc.

Examples of cosmetic tool applications include cosmetic puffs and eye color chips.
For various miscellaneous goods, bath products such as bath pillows, massage puffs, mouth pads, armrests for keyboards, non-slip cushions, stationery (pen grips, penetrating stamps), small pillows for desks, ear plugs, cotton sticks, sheets for hot packs. , Cold pack sheet, wet cloth, glasses pad, underwater eyeglass pad, face protector, watch pad, headphone ear pad, earphone, ice pillow cover, core material such as folding pillow, cushion material, skin material, skin lining material, both sides Examples thereof include a tape base material, an fragrance, and an adsorption medium such as a stamp stand.

Examples of clothing applications include pad materials such as shoulders and brassieres, liners such as cold protection materials, and heat insulating materials.

For sports applications, sports protectors, bouldering (climbing mini rock climbing 2 to 3 m rock climbing) mats, beat boards, cushioning materials for high jumps, landing mats for gymnastics and exercise, kids mats, etc. Examples include materials, skin materials, skin lining materials, liners for ski boots, snowboard boots, and the like.

For toys and playground equipment, hand exercisers, healing goods, key chains, stuffed animals, mannequin bodies, balls, massage balls and other cushioning materials and fillings, skin materials and skin lining materials, ornaments and monsters and other special shapes, etc. Examples include casting materials for molding the shape of articles and making models, molding materials for shaping articles in the casting method, materials for making model samples from molds, materials for making ornaments, special moldings and molded objects for monsters, etc. ..

The resin composition used for forming the foam preferably contains a base resin (A), a chemical foaming agent (B), and a silanol condensation catalyst (D).
The base resin (A) has a reactive silicon group. The base resin (A) preferably contains a polyoxyalkylene polymer (A1) and an acrylic resin (A2) having a glass transition temperature of 35 ° C. or higher in combination.
Hereinafter, essential or optional components contained in the foam resin composition will be described in detail.

<Base resin (A)>
The base resin (A) is a curable component having a reactive silicon group. The base resin (A) preferably has at least one reactive silicon group in the molecular chain.
Since (A) has a reactive silicon group in the base resin, a silanol condensation reaction occurs between the reactive silicon groups to crosslink the resin, and the resin becomes a polymer state and is cured.
The base resin (A) contains a polyoxyalkylene polymer (A1) as a resin having a reactive silicon group. The foam contains a cured product in which the polyoxyalkylene polymer (A1) is cured by a condensation reaction between reactive silicon groups, and the foaming state is appropriately adjusted to exhibit desired sound absorbing characteristics.
The number of reactive silicon groups contained in the base resin (A) is preferably at least one in the molecular chain from the viewpoint of condensation reactivity. From the viewpoint of curability and flexibility, the base resin (A) is preferably a polymer having reactive silicon groups at both ends of the main chain or the molecular chain at the branch portion. The number of such polymers is preferably 1.0 or more and 3.0 or less, more preferably 1.1 or more and 2.5 or less, and particularly preferably 1.2 or more and 2.0 or less in one molecule. It has a reactive silicon group.
The curing reaction of the base resin (A) by the reaction between the reactive silicon groups can proceed sufficiently only by the moisture in the air and the material. Therefore, even when the foam resin composition used for producing the foam does not contain water (C) or contains a very small amount of water (C), the foam resin composition There is no particular problem in terms of the progress of curing.

When the base resin (A) consists only of a polymer having reactive silicon groups at both ends of the main chain or the molecular chain at the branching portion, the acetone gel fraction of the obtained foam tends to be high. A high acetone gel fraction means that the foam has high organic solvent resistance. When the acetone gel content of the foam is high, for example, when the foam is applied to various buildings or attached to various devices by using an adhesive containing an organic solvent, the solvent of the foam is used. Deterioration (elution of solvent-soluble components) is unlikely to occur.

Further, the base resin (A) contains a polymer having a reactive silicon group at both ends of the main chain or the molecular chain at the branch portion, and a polymer having a reactive silicon group only at one end of the molecular chain. You may. The number of polymers having a reactive silicon group at only one end of the molecular chain is preferably 1.0 or less, more preferably 0.3 or more and 1.0 or less, still more preferably, on average in one molecule. It has 0.4 or more and 1.0 or less, particularly preferably 0.5 or more and 1.0 or less reactive silicon groups.
The content of the polymer having reactive silicon groups at both ends of the molecular chain in 100 parts by weight of the base resin (A) is preferably 65 parts by weight or more and 95 parts by weight or less. The content of the polymer having a reactive silicon group only at one end of the molecular chain in 100 parts by weight of the base resin (A) is preferably 5 parts by weight or more and 35 parts by weight or less.

The reactive silicon group contained in the base resin (A) has a hydroxy group or a hydrolyzable group bonded to a silicon atom, and is crosslinked by forming a siloxane bond by a reaction accelerated by a silanol condensation catalyst. It is a possible group. As the reactive silicon group, the formula (1a):
-Si (R ^1a ) _3-a (X) _a (1a)
(R ^1a is independently a hydrocarbon group having 1 or more and 20 or less carbon atoms, or -OSi (R') ₃ (R'is independently a hydrocarbon group having 1 or more and 20 or less carbon atoms. ), And the hydrocarbon group as R ^1a may be substituted and may have a hetero-containing group, and X is independently a hydroxy group or a hydro group. It is a degradable group. Further, a is an integer of 1 or more and 3 or less)
The group represented by is mentioned.

The hydrolyzable group is not particularly limited, and any conventionally known hydrolyzable group may be used. Specific examples thereof include hydrogen atom, halogen atom, alkoxy group, acyloxy group, ketoximate group, amino group, amide group, acid amide group, aminooxy group, mercapto group, alkenyloxy group and the like. Among these, a hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group, and an alkenyloxy group are preferable, and alkoxy is preferable from the viewpoint of mild hydrolyzability and easy handling. Groups are particularly preferred.

The hydrolyzable group and the hydroxy group can be bonded to one silicon atom in the range of 1 or more and 3 or less. When two or more hydrolyzable groups or hydroxy groups are bonded to the reactive silicon group, they may be the same or different.

The a in the above formula (1a) is preferably 2 or 3, and is preferably 3 from the viewpoint of curability and the point that curing and foaming proceed at the same time.

Specific examples of R ^1a in the above formula (1a) include alkyl groups such as methyl group and ethyl group, cycloalkyl groups such as cyclohexyl group, aryl groups such as phenyl group, aralkyl groups such as benzyl group, and R. 'Is a methyl group, a phenyl group, etc.-A triorganosyloxy group, a chloromethyl group, a methoxymethyl group, etc. represented by -OSi (R') ₃ can be mentioned. Of these, a methyl group and a methoxymethyl group are particularly preferable.

More specific examples of the reactive silicon group represented by the above formula (1a) include a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group, a dimethoxymethylsilyl group, a diethoxymethylsilyl group, and a diethoxymethylsilyl group. Examples thereof include an isopropoxymethylsilyl group and a (methoxymethyl) dimethoxysilyl group. A trimethoxysilyl group, a triethoxysilyl group, and a dimethoxymethylsilyl group are preferable, and a trimethoxysilyl group is more preferable, because high activity and good curability can be obtained.

The structure of the base resin (A) may be linear or has a branched structure, but the branched structure is preferable from the viewpoint of curability. When the main chain structure of the base resin (A) is a branched structure, the base resin (A) preferably has three or more ends.

The molecular weight of the base resin (A) is preferably 1500 or more, more preferably 3000 or more, as the number average molecular weight Mn from the viewpoint of the balance between viscosity and reactivity. The upper limit of the number average molecular weight Mn is not particularly limited, but is preferably 50,000 or less, more preferably 30,000 or less, and even more preferably 20,000 or less. Further, the base resin (A) may be a combination of two or more types. At that time, the polymer other than the polymer used as the main agent may be other than the above conditions if the purpose is to adjust the viscosity and the crosslinked structure.

The reactive silicon group at the terminal of the base resin (A) can be introduced by terminal-modifying the oxyalkylene at the terminal of the hydroxy group with an isocyanate silane compound. As another method, a reactive silicon group is introduced at the terminal of the base resin (A) by introducing a group having a carbon-carbon unsaturated bond such as an allyl group at the terminal of the hydroxy group and then hydrosilylating with alkoxysilane. Can also be introduced. Further, when the terminal of the polyisocyanate-modified product is an isocyanate group, a reactive silicon group can be introduced into the terminal of the base resin (A) by terminal-modifying with aminosilane having active hydrogen or the like.

As the reactive silicon group or the terminal group containing the reactive silicon group in the base resin (A) described above, a trimethoxysilyl group (methoxymethyl) can be easily produced as a foam having a high expansion ratio. Dimethoxysilyl group, formulas (1) to (3) below:

(In formulas (1) to (3), R ¹ is independently a hydrocarbon group having 1 or more and 20 or less carbon atoms, and the hydrocarbon group as R ¹ may be substituted. It may have a hetero-containing group, where X is a hydroxy or hydrolyzable group, a is 1, 2, or 3, R ⁴ is a divalent linking group, and R ⁴ has two. The bonders are bonded to carbon atoms, oxygen atoms, nitrogen atoms, or sulfur atoms in the linking group, respectively, and R ² and R ³ are independently hydrogen atoms and carbon atoms of 1 to 20 or less, respectively. It is either an alkyl group, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a silyl group.)
The group represented by and the following formula (4):
-R ^5- CH _2- Si (R ¹ ) _3-a (X) _a (4)
(In the formula (4), ^{R 1,} and a is the same as ^{R 1,} and a in equation (1) to (3), ^{R 5} is a hetero atom which may be substituted.)
The group represented by is preferable.

In the structure represented by formula (1) to (3), as mentioned ^above, the reactive silicon group represented by _{-Si (R 1) 3-a} (X) a, carbon - carbon double bond Adjacent. Therefore, in the structures represented by the formulas (1) to (3), the carbon-carbon double bond acts as an electron-withdrawing group, and the activity of the reactive silicon group is improved. As a result, the base resin (A) having a terminal group represented by the formulas (1) to (3) and the foam resin composition containing the base resin (A) are said to have excellent curing reactivity. Conceivable.

R ⁴ is a divalent linking group. The two bonds of R ⁴ are bonded to a carbon atom, an oxygen atom, a nitrogen atom, or a sulfur atom in the linking group, respectively.
Here, the two bonds possessed by R ⁴ are bonded to the carbon atom, oxygen atom, nitrogen atom, or sulfur atom in the linking group, respectively, and the two bonds possessed by R ⁴ are respectively. It means that it exists on a carbon atom, an oxygen atom, a nitrogen atom, or a sulfur atom in a linking group.
Specific examples of the divalent linking _{_{_{_{group, - (CH 2) n -}}}} , - O- (CH 2) n -, - S- (CH 2) n -, - NR 8 - (CH 2) n -, ^{-O-C (= O) -NR} 8 - (CH 2) n -, and ^{^{-NR 8 -C (= O) -NR}} 8 - (CH 2) n -, it includes like. Among _{_{these, -O- (CH 2) n -}} , - O-C (= O) -NR 8 - (CH 2) n -, and ^{^{-NR 8 -C (= O) -NR}} 8 - (CH ₂ ) _n -is preferable, and -O-CH _2- is more preferable because the raw material is easily available. R ⁸ is a hydrogen atom or a hydrocarbon group having 1 or more and 10 or less carbon atoms. Examples of the hydrocarbon group as R ⁸ include an alkyl group such as a methyl group, an ethyl group, an n-propyl group and an isopropyl group, an aryl group such as a phenyl group and a naphthyl group, and an aralkyl group such as a benzyl group. Be done. As n, an integer of 0 or more and 10 or less is preferable, an integer of 0 or more and 5 or less is more preferable, an integer of 0 or more and 2 or less is further preferable, 0 or 1 is particularly preferable, and 1 is most preferable.

R ² and R ³ are independently hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and a silyl group. It is either. The number of carbon atoms of the alkyl group is preferably 1 or more and 12 or less, more preferably 1 or more and 6 or less, and particularly preferably 1 or more and 4 or less. The number of carbon atoms of the aryl group is preferably 6 or more and 12 or less, and more preferably 6 or more and 10 or less. The number of carbon atoms of the aralkyl group is preferably 7 or more and 12 or less.
Specific examples of R ² and R ³ include hydrogen; alkyl groups such as methyl group, ethyl group, and cyclohexyl; aryl groups such as phenyl group and tolyl group; aralkyl groups such as benzyl group and phenethyl group. A silyl group such as a trimethylsilyl group can be mentioned. Among these, hydrogen, a methyl group, and a trimethylsilyl group are preferable, hydrogen and a methyl group are more preferable, and hydrogen is further preferable.

The structures represented by the above formulas (1) to (3) include the following formulas (5) to (7):

The structure represented by is preferable.
R ¹ , X, and a are the same as described above.

In the formulas (1) to (4), the hydrocarbon group as R ^{1 is the same} as the hydrocarbon group as R ^1a in the formula (1a).
Examples of the hydrocarbon group as R ¹ include an alkyl group such as a methyl group and an ethyl group; an alkyl group having a hetero-containing group such as a chloromethyl group and a methoxymethyl group; a cycloalkyl group such as a cyclohexyl group; phenyl. An aryl group such as a group; an aralkyl group such as a benzyl group; and the like can be mentioned. The R ^1, a methyl group, methoxymethyl group, and a chloromethyl group are preferred, a methyl group, and more preferably a methoxymethyl group, methoxymethyl group are more preferred.

The X in the formulas (1) to (4) is as described above for the formula (1a).

R ⁵ in formula (4) is a heteroatom that may be substituted. Since R ⁵ is an electron-rich heteroatom, the terminal group having a reactive silicon group represented by the formula (4) exhibits high reactivity.
The optionally substituted hetero atom as R ⁵ in the formula (4) is not particularly limited so long as it does not inhibit the object of the present invention. Specific examples of the heteroatom include O, N, and S.
When R ⁵ is an unsubstituted heteroatom, specific examples of the divalent group represented by -R ^5- include -O- and -S-.
When R ⁵ is a substituted heteroatom, specific examples of the divalent group represented by -R ^5- include, for example, -SO-, -SO _2- , -NH-, and -NR ^6-. Can be mentioned.
R ⁶ as a substituent is not particularly limited. Preferable examples of R ⁶ include a hydrocarbon group, an acyl group represented by -CO-R ⁷ , and the like. A hydrocarbon group is preferable as R ⁷ . Examples of the hydrocarbon groups as R ⁶ and R ^{7 are the same} as those of the hydrocarbon groups as R ¹ .

The main chain structure of the base resin (A) will be described below.

[Main chain structure]
As described above, the main chain structure of the base resin (A) may be linear or may have a branched chain.
The main chain structure of the base resin (A) is not particularly limited. As the base resin (A), a polymer containing a main chain skeleton having various main chain structures can be used.
Examples of the polymer constituting the main chain skeleton of the base resin (A) include a polyoxyalkylene polymer, a hydrocarbon polymer, a polyester polymer, a vinyl (co) polymer, and (meth) acrylic. Acid ester-based (co) polymer, graft polymer, polysulfide-based polymer, polyamide-based polymer, polycarbonate-based polymer, polymer having urethane bond and / or urea bond (urethane prepolymer), diallyl phthalate-based polymer Etc. can be given.
As described above, the base resin (A) preferably contains a polyoxyalkylene polymer (A1) and an acrylic resin (A2) having a glass transition temperature of 35 ° C. or higher.

Examples of the polyoxyalkylene polymer include polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, and polyoxypropylene-polyoxybutylene copolymer. And so on.

Examples of the hydrocarbon-based polymer include ethylene-propylene-based copolymers, polyisobutylene, copolymers of isobutylene and isoprene, polychloroprene, polyisoprene, isoprene or butadiene and acrylonitrile and / or styrene and the like. Examples thereof include coalescing, polybutadiene, isoprene, or copolymers of butadiene with acrylonitrile and styrene, and hydrocarbon-based polymers obtained by hydrogenating these polyolefin-based polymers.

Examples of the polyester-based polymer include polymers having an ester bond such as a polymer obtained by a condensation reaction of a dibasic acid such as adipic acid and a glycol, and a polymer obtained by ring-opening polymerization of lactones. Be done.

The vinyl-based (co) polymer is obtained by radical polymerization of, for example, vinyl-based monomers such as (meth) acrylic acid ester, vinyl acetate, acrylonitrile, and styrene, alone or in combination of two or more (co). Polymers can be mentioned.

Examples of the (meth) acrylic acid ester-based (co) polymer include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and (meth) acrylate. ) Examples thereof include (co) polymers obtained by radical polymerization of (meth) acrylic acid ester monomers such as stearyl acrylate, alone or in combination of two or more. The (meth) acrylic acid ester-based (co) polymer is a so-called acrylic resin.
In the specification and claims of the present application, the "acrylic resin" is not limited to a polymer of a monomer composed of acrylic acid and / or an acrylic acid derivative. Within the specification and claims of the present application, a polymer of a monomer containing methacrylic acid and / or a methacrylic acid derivative is also included in the "acrylic resin".

Examples of the graft polymer include a polymer obtained by polymerizing a vinyl-based monomer among the above-mentioned various polymers.

Examples of the polyamide polymer include nylon 6 obtained by ring-opening polymerization of ε-caprolactam, nylon 6.6 obtained by condensation polymerization of hexamethylenediamine and adipic acid, and condensation polymerization of hexamethylenediamine and sebacic acid. Nylon 6/10 obtained, nylon 11 obtained by condensation polymerization of ε-aminoundecanoic acid, nylon 12 obtained by ring-opening polymerization of ε-aminolaurolactum, and a combination of two or more of the above nylon components. Polymerized nylon and the like can be mentioned.

Examples of the polycarbonate-based polymer include a polymer produced by polycondensation of bisphenol A and carbonyl chloride.

Examples of the polymer having a urethane bond and / or a urea bond (urethane prepolymer) include a liquid polymer compound having an isocyanate group at the molecular terminal obtained by reacting a polyol with an excessive amount of a polyisocyanate compound. Be done.

In the specification of the present application, "(meth) acrylate" means "acrylate and / or methacrylate". "(Meta) acrylic acid" means "acrylic acid and / or methacrylic acid". The "(co) polymer" means a "polymer and / or a copolymer".

Among the polymers constituting the main chain skeleton of the base resin (A), saturated hydrocarbon-based polymers such as polyisobutylene, hydrogenated polyisoprene, and hydrogenated polybutadiene, polyoxyalkylene-based polymers, and acrylic resins. ((Meta) acrylic acid ester-based polymer) is preferable because the glass transition temperature is relatively low and the obtained cured product has excellent cold resistance.

Hereinafter, the glass transition temperature of the base resin (A) will be described.
The glass transition temperature of the polymer constituting the main chain skeleton of the base resin (A) is not particularly limited, but is preferably 20 ° C. or lower, more preferably 0 ° C. or lower, and −20 ° C. or lower. Is particularly preferable. If the glass transition temperature exceeds 20 ° C., the viscosity of the resin composition for foam in winter or cold regions may increase, which may result in poor workability, and the flexibility of the foam may decrease, resulting in elongation. May decrease. The glass transition temperature shows the value measured by DSC.

It is also preferable that the base resin (A) contains a resin having a glass transition temperature of 35 ° C. or higher. In this case, it is easy to suppress the shrinkage of the foam after foaming. From the viewpoint that shrinkage of the foam after foaming is particularly easy to be suppressed, the base resin (A) contains a resin having a glass transition temperature of 35 ° C. or higher and a resin having a glass transition temperature of less than 35 ° C. preferable.
The glass transition temperature of the above-mentioned polyoxyalkylene polymer (A1) is usually less than 35 ° C. Therefore, the polyoxyalkylene polymer (A1) can be suitably used as a resin having a glass transition temperature of less than 35 degrees.
Since a particularly good shrink suppressing effect can be obtained, the glass transition temperature of the resin having a glass transition temperature of less than 35 ° C. is preferably 20 ° C. or lower, more preferably −10 ° C. or lower. A resin having a glass transition temperature of less than 35 ° C can dissolve a resin having a glass transition temperature of 35 ° C or higher. A foam with a small amount of cross-linking component can be obtained.
The glass transition temperature of the base resin (A) can be adjusted by adjusting the type of the main chain skeleton, the type of the unit constituting the main chain, the composition of the unit constituting the main chain, the molecular weight, and the like.
The glass transition temperature of the resin having a glass transition temperature of 35 ° C. or higher is preferably 35 ° C. or higher and 180 ° C. or lower, and more preferably 50 ° C. or higher and 120 ° C. or lower.
The lower limit of the glass transition temperature of the resin having a glass transition temperature of less than 35 ° C. is preferably −60 ° C. or higher, more preferably −30 ° C. or higher.
As the resin having a glass transition temperature of 35 ° C. or higher, an acrylic resin (A2) is preferable because it is particularly easy to suppress shrinkage of the foam. That is, the base resin (A) having a reactive silicon group used in the production of the foam is a polyoxyalkylene polymer (A1) and an acrylic resin (A2) having a glass transition temperature of 35 ° C. or higher. It is preferable to include them in combination.
The glass transition temperature of the base resin (A) can be adjusted by adjusting the type of the main chain skeleton, the type of the unit constituting the main chain, the composition of the unit constituting the main chain, the molecular weight, and the like.

Among the polymers constituting the main chain skeleton of the base resin (A), the polyoxyalkylene polymer (A1) and the acrylic resin (A2) are preferable because of their high moisture permeability. Among the polyoxyalkylene-based polymer (A1) as an essential component, the polyoxypropylene-based polymer is preferable.
When the base resin (A) contains an acrylic resin (A2) and a polyoxyalkylene polymer (A1), a base resin composition having a viscosity within an appropriate range can be easily obtained. The amount of acrylic resin (A2) in 100 parts by weight of the resin (A) is preferably 3 parts by weight or more and 80 parts by weight or less, more preferably 10 parts by weight or more and 80 parts by weight or more, and 10 parts by weight or more and 50 parts by weight or less. More preferably, it is more preferably 5 parts by weight or more and 50 parts by weight or less, particularly preferably 5 parts by weight or more and 30 parts by weight or less, and most preferably 10 parts by weight or more and 30 parts by weight or less.
When the base resin (A) has a low viscosity, it is easy to stir the foam resin composition when producing the foam. When the base resin (A) has a low viscosity, particularly when the resin composition for a foam is a two-component or more multi-component composition, a static mixer or the like for each liquid during foam production. It is easy to mix uniformly with. From this point as well, the content of the acrylic resin (A2) in the described resin (A) is preferably an amount within the above range.

The reactive silicon group may be introduced into the main chain of the base resin (A) by a known method. For example, the following method can be mentioned.

Method I: An organic polymer having a functional group such as a hydroxy group is reacted with a compound having an active group and an unsaturated group exhibiting reactivity with this functional group to obtain an organic polymer having an unsaturated group. Then, the obtained organic polymer having an unsaturated group is reacted with a hydrosilane compound having a reactive silicon group by hydrosilylation.

Examples of the reactive compound having an active group and an unsaturated group that can be used in Method I include an unsaturated group-containing epoxy compound such as allyl glycidyl ether, allyl chloride, metallic chloride, vinyl bromide, and allyl bromide. Examples thereof include compounds having a carbon-carbon double bond such as metallyl bromide, vinyl iodide, allyl iodide, and metallyl iodide.
Examples of the compound having a carbon-carbon triple bond include propargyl chloride, 1-chloro-2-butyne, 4-chloro-1-butyne, 1-chloro-2-octyne, 1-chloro-2-pentin, 1, 4-Dichloro-2-butyne, 5-chloro-1-pentin, 6-chloro-1-hexine, propargyl bromide, 1-bromo-2-butyne, 4-bromo-1-butyne, 1-bromo-2- Octin, 1-bromo-2-pentin, 1,4-dibromo-2-butyne, 5-bromo-1-pentin, 6-bromo-1-hexine, propargyl iodide, 1-iodo-2-butyne, 4- Iodo-1-butyne, 1-iodo-2-octyne, 1-iodo-2-pentin, 1,4-diiodo-2-butyne, 5-iodo-1-pentyne, 6-iodo-1-hexine, etc. Examples thereof include halogenated hydrocarbon compounds having a carbon-carbon triple bond. Of these, propargyl chloride, propargyl bromide, and propargyl iodide are more preferred.
At the same time as a halogenated hydrocarbon compound having a carbon-carbon triple bond, vinyl chloride, allyl chloride, metallyl chloride, vinyl bromide, allyl bromide, metallyl bromide, vinyl iodide, allyl iodide, metallyl iodide, etc. Hydrocarbon compounds having unsaturated bonds other than halogenated hydrocarbons having carbon-carbon triple bonds may be used.

Examples of the hydrosilane compound that can be used in Method I include halogenated silanes, alkoxysilanes, asyloxysilanes, and ketoximatesilanes. Hydrosilane compounds are not limited to these.

Examples of halogenated silanes include trichlorosilane, methyldichlorosilane, dimethylchlorosilane, and phenyldichlorosilane.

Examples of alkoxysilanes include trimethoxysilane, triethoxysilane, triisopropoxysilane, dimethoxymethylsilane, diethoxymethylsilane, diisopropoxymethylsilane, (methoxymethyl) dimethoxysilane, phenyldimethoxysilane, and 1-. [2- (Trimethoxysilyl) ethyl] -1,1,3,3-tetramethyldisiloxane and the like can be mentioned.

Examples of asyloxysilanes include methyldiacetoxysilane and phenyldiacetoxysilane.

Examples of ketoximate silanes include bis (dimethyl ketoximate) methylsilane and bis (cyclohexylketoximate) methylsilane.

Among these, halogenated silanes and alkoxysilanes are particularly preferable. Alkoxysilanes are most preferred because they are mildly hydrolyzable and easy to handle.

Among the alkoxysilanes, a foam having excellent tensile strength is produced by using the resin composition for foam, which is easily available, has excellent curability and storage stability, and is easy to obtain. Dimethoxymethylsilane is preferable because it is easy to use. Further, trimethoxysilane and triethoxysilane are also preferable from the viewpoint that a resin composition for a foam having excellent curability can be easily obtained.

Method II: An organic polymer having an unsaturated group obtained by subjecting a compound having a mercapto group and a reactive silicon group to a radical addition reaction in the presence of a radical initiator and / or a radical source in the same manner as in Method I. Method of introducing into the unsaturated radical site of.

Examples of the compound having a mercapto group and a reactive silicon group that can be used in Method II include 3-mercapto-n-propyltrimethoxysilane, 3-mercapto-n-propylmethyldimethoxysilane, and 3-mercapto-n-propyl. Examples thereof include triethoxysilane, 3-mercapto-n-propylmethyldiethoxysilane, mercaptomethyltrimethoxysilane, and mercaptomethyltriethoxysilane. Compounds having a mercapto group and a reactive silicon group are not limited thereto.

Method III: An organic polymer having a functional group such as a hydroxy group, an epoxy group, and an isocyanate group in the molecule is reacted with a compound having a functional group exhibiting reactivity with these functional groups and a reactive silicon group. Method.

The method for reacting the organic polymer having a hydroxy group with the compound having an isocyanate group and a reactive silicon group, which can be adopted in Method III, is not particularly limited, but is shown in, for example, JP-A-3-47825. There is a method to be used.

Examples of the compound having an isocyanate group and a reactive silicon group that can be used in Method III include 3-isocyanato-n-propyltrimethoxysilane, 3-isocyanato-n-propylmethyldimethoxysilane, and 3-isocyanato-n-. Examples thereof include propyltriethoxysilane, 3-isocyanato-n-propylmethyldiethoxysilane, isocyanatomethyltrimethoxysilane, isocyanatomethyltriethoxysilane, isocyanatomethyldimethoxymethylsilane, and isocyanatomethyldiethoxymethylsilane. .. Compounds having an isocyanate group and a reactive silicon group are not limited thereto.

A silane compound in which three hydrolyzable groups are bonded to one silicon atom such as trimethoxysilane may undergo a disproportionation reaction. As the disproportionation reaction proceeds, unstable compounds such as dimethoxysilane are produced, which may be difficult to handle. However, such disproportionation reaction does not proceed with 3-mercapto-n-propyltrimethoxysilane or 3-isocyanato-n-propyltrimethoxysilane. Therefore, when a group in which three hydrolyzable groups such as a trimethoxysilyl group are bonded to one silicon atom is used as the silicon-containing group, the method of Method II or Method III is preferably used.

On the other hand, the disproportionation reaction does not proceed with the silane compound represented by the following formula (2a).
H- (SiR ^2a ₂ O) _m SiR ^2a _2- R ^3a- SiX ₃ (2a)
Here, in the formula (2a), X is the same as the formula (1a). The 2m + 2 R ^2a are independently the same as the R ^1a of the equation (1a). R ^3a represents a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms. m indicates an integer of 0 or more and 19 or less.

Therefore, when introducing a group in which three hydrolyzable groups are bonded to one silicon atom in Method I, it is preferable to use the silane compound represented by the formula (2a). From the viewpoint of availability and cost, each of the 2m + 2 R ^2a is preferably a hydrocarbon group having 1 to 20 carbon atoms, more preferably a hydrocarbon group having 1 to 8 carbon atoms, and carbon. Hydrocarbon groups having 1 or more and 4 or less atoms are more preferable. As R ^3a , a divalent hydrocarbon group having 1 to 12 carbon atoms is preferable, a divalent hydrocarbon group having 2 to 8 carbon atoms is more preferable, and a divalent hydrocarbon having 2 carbon atoms is preferable. Groups are even more preferred. The m is most preferably 1.

Examples of the silane compound represented by the formula (2a) include 1- [2- (trimethoxysilyl) ethyl] -1,1,3,3-tetramethyldisiloxane and 1- [2- (trimethoxysilyl). Examples thereof include propyl] -1,1,3,3-tetramethyldisiloxane and 1- [2- (trimethoxysilyl) hexyl] -1,1,3,3-tetramethyldisiloxane.

In the above method I or method III, the method of reacting the organic polymer having a hydroxy group at the terminal with the compound having an isocyanate group and a reactive silicon group can obtain a high conversion rate in a relatively short reaction time. Is preferable. Further, the organic polymer having a reactive silicon group obtained by Method I has a lower viscosity than the organic polymer having a reactive silicon group obtained by Method III, and is a resin composition for a foam having good workability. The method I is particularly preferable because the organic polymer having a reactive silicon group obtained by the method II has a strong odor based on mercaptosilane.

Hereinafter, a polyoxyalkylene polymer (A1) having a reactive silicon group and an acrylic resin ((meth) acrylic acid ester copolymer) (A2), which are essential or particularly preferable among the base resin (A), are used. ) Will be described in detail.

(Polyoxyalkylene polymer (A1))
The main chain structure of the polyoxyalkylene polymer (A1) preferably comprises a repeating unit represented by the following formula (3a).
-R ^4a -O- (3a)
Here, in the formula (3a), R ^4a represents a linear or branched alkylene group having 1 or more and 14 or less carbon atoms, and more preferably 2 or more and 4 or less carbon atoms.

The repeating unit represented by formula (3a), for _{_{_{_{example, -CH 2 O -, - CH}}}} 2 CH 2 O -, - CH 2 CH (CH 3) O -, - CH 2 CH (C 2 H 5) O -, -CH ₂ C (CH ₃ ) ₂ O-, -CH ₂ CH ₂ CH ₂ CH ₂ O- and the like can be mentioned.

The main chain of the polyoxyalkylene polymer (A1) may consist of only one type of repeating unit or may consist of two or more types of repeating units. The polyoxyalkylene polymer (A1) is preferably an amorphous polyoxypropylene polymer having a relatively low viscosity.

Examples of the method for synthesizing the polyoxyalkylene polymer (A1) include a polymerization method using an alkali catalyst such as KOH; a complex obtained by reacting an organic aluminum compound shown in JP-A-61-215623 with porphyrin and the like. Transition metal compound-porphyrin complex-catalyzed polymerization method; JP-A-46-27250, JP-A-59-15336, US Pat. No. 3,278,457, US Pat. No. 3,278,458, US Pat. No. 3,278,459, US Pat. No. 3,427,256, USA Polymerization method using a composite metal cyanide complex catalyst (for example, zinc hexacyanocobaltate glyme complex catalyst) shown in Japanese Patent No. 3427334 and US Patent No. 3427335; a catalyst composed of a polyphosphazene salt shown in JP-A-10-273512. ; A polymerization method using a catalyst composed of a phosphazene compound shown in JP-A-11-060722. The method for synthesizing the polyoxyalkylene polymer (A1) is not limited to these.

Among these synthetic methods, a polymerization method in which an alkylene oxide is reacted with an initiator in the presence of a composite metal cyanide complex catalyst is preferable because a polymer having a narrow molecular weight distribution can be obtained.

Examples of the composite metal cyanide complex catalyst include Zn ₃ [Co (CN) ₆ ] ₂ (zinc hexacyanocobaltate complex). Further, a catalyst in which alcohol and / or ether is coordinated as an organic ligand can also be used.

As the initiator, a compound having at least two active hydrogen groups is preferable. Examples of the active hydrogen-containing compound include polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, and glycerin, and linear or branched polyether compounds having a number average molecular weight of 500 or more and 20,000 or less.

Examples of the alkylene oxide include ethylene oxide, propylene oxide, and isobutylene oxide.

Examples of the polyoxyalkylene polymer (A1) having a reactive silicon group include JP-A-45-363319, JP-A-46-12154, JP-A-50-156599, and JP-A-54-. 6096, Japanese Patent Application Laid-Open No. 55-13767, Japanese Patent Application Laid-Open No. 55-13468, Japanese Patent Application Laid-Open No. 57-164123, Japanese Patent Application Laid-Open No. 3-2450, US Pat. No. 363255, US Pat. No. 4345053, US Pat. Examples thereof include polymers proposed in Japanese Patent No. 4366307, US Pat. No. 4,960,844, and the like. Further, Japanese Patent Application Laid-Open No. 61-197631, Japanese Patent Application Laid-Open No. 61-215622, Japanese Patent Application Laid-Open No. 61-215623, Japanese Patent Application Laid-Open No. 61-218632, Japanese Patent Application Laid-Open No. 3-72527, JP-A-3-72527 Molecular weight distribution with a number average molecular weight of 6,000 or more and a molecular weight distribution (Mw / Mn) of 1.6 or less or 1.3 or less proposed in each of Japanese Patent Application Laid-Open No. 47825 and Japanese Patent Application Laid-Open No. 8-231707. A polyoxyalkylene polymer having a narrow reactive silicon group or the like is also preferable. The polyoxyalkylene polymer (A1) having such a reactive silicon group may be used alone or in combination of two or more.

(Acrylic resin ((meth) acrylic acid ester-based (co) polymer) (A2))
Acrylic resin having a reactive silicon group (((meth) acrylic acid ester-based (co) polymer) (A2) is obtained by polymerizing various (meth) acrylic acid ester-based monomers alone or in combination of two or more. Can be obtained by

Examples of the (meth) acrylic acid ester-based monomer include (meth) acrylic acid, methyl (meth) acrylic acid, ethyl (meth) acrylic acid, n-propyl (meth) acrylic acid, and isopropyl (meth) acrylic acid. , (Meta) n-butyl acrylate, (meth) isobutyl acrylate, (meth) tert-butyl acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate , (Meta) n-heptyl acrylate, (meth) n-octyl acrylate, (meth) 2-ethylhexyl acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate (meth) ) Phenyl acrylate, toluyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, ( 2-Hydroxypropyl acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate, 2-aminoethyl (meth) acrylate, 3-((meth) acryloyloxy) -n-propyltrimethoxysilane, 3-((Meta) Acryloyloxy) -n-propyldimethoxymethylsilane, (Meta) Acryloyloxymethyltrimethoxysilane, (Meta) Acryloyloxymethyltriethoxysilane, (Meta) Acryloyloxymethyldimethoxymethylsilane, (Meta) Examples thereof include (meth) acrylic acid-based monomers such as acryloyloxymethyldiethoxymethylsilane and an ethylene oxide adduct of (meth) acrylic acid. The (meth) acrylic acid ester-based monomer is not limited to these.

The acrylic resin (A2) can also be copolymerized with the following vinyl-based monomer together with the (meth) acrylic acid ester-based monomer.

Examples of the vinyl-based monomer include styrene-based monomers such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid, and styrenesulfonate; vinyltrimethoxysilane and vinyltriethoxysilane. Silicon-containing vinyl-based monomers such as; maleic anhydride, maleic acid, and maleic acid or maleic acid derivatives such as maleic acid monoalkyl esters and dialkyl esters; fumaric acid, and fumaric acid monoalkyl esters and dialkyl esters, etc. Fumaric acid or fumaric acid derivative; maleimide-based monomers such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, and cyclohexylmaleimide; acrylonitrile, And nitrile group-containing vinyl monomers such as methacrylonitrile; acrylamide and amide group-containing vinyl monomers such as methacrylicamide; vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, and vinyl cinnate. Vinyl esters such as; alkens such as ethylene and propylene; conjugated dienes such as butadiene and isoprene; vinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol and the like. These may be polymerized alone, or a plurality of them may be copolymerized.

The acrylic resin (A2) is a (co) polymer of a (meth) acrylic acid ester-based monomer or a copolymer of a styrene-based monomer and a (meth) acrylic acid-based monomer from the viewpoint of physical properties and the like. Is preferable, a (co) polymer of a (meth) acrylic acid ester-based monomer is more preferable, and a (co) polymer of an acrylic acid ester-based monomer is further preferable.

The method for producing the acrylic resin (A2) is not particularly limited. The (meth) acrylic acid ester-based (co) polymer can be produced by a known method. However, a polymer obtained by a normal free radical polymerization method using an azo compound, a peroxide or the like as a polymerization initiator generally has a molecular weight distribution value of more than 2, and tends to have a high viscosity. Therefore, it is a (meth) acrylic acid ester-based (co) polymer having a narrow molecular weight distribution and low viscosity, and has a high proportion of crosslinkable functional groups at the ends of the molecular chain (meth) acrylic acid ester-based (co) weight. In order to obtain coalescence, it is preferable to use the living radical polymerization method.

Among the "living radical polymerization methods", "atom transfer radicals" that polymerize (meth) acrylic acid ester-based monomers using organic halides, sulfonyl halide compounds, etc. as initiators and transition metal complexes as catalysts. In addition to the above-mentioned features of the "living radical polymerization method", the "polymerization method" has a halogen or the like at the end, which is relatively advantageous for the functional group conversion reaction, and has a large degree of freedom in designing the initiator and catalyst. It is more preferable as a method for producing an acrylic resin (A2) having a specific functional group. This atom transfer radical polymerization method is described, for example, in Mattyjaszewski et al., Journal of the American Chemical Society (J. Am. Chem. Soc), 1995, Vol. 117, p. 5614.

As a method for producing an acrylic resin (A2) having a reactive silicon group, for example, JP-A-314068, JP-A-4-55444, JP-A-6-21922, etc., refer to a chain transfer agent. A production method using the free radical polymerization method used is disclosed. Further, Japanese Patent Application Laid-Open No. 9-272714 and the like disclose a production method using an atom transfer radical polymerization method. The method for producing a (meth) acrylic acid ester-based (co) polymer having a reactive silicon group is not limited to these methods. The (meth) acrylic acid ester-based (co) polymer having the above-mentioned reactive silicon group may be used alone or in combination of two or more.

The base resin (A) having these reactive silicon groups may be used alone or in combination of two or more. Specifically, when two or more types of base resin (A) are used in combination, the base resin (A) having the same type of main chain may be used in combination, for example, a polymer having a reactive silicon group. A base resin (A) having a different main chain is used in combination, such as a combination of an oxyalkylene polymer (A1) and a (meth) acrylic acid ester polymer having a reactive silicon group (A2). You may.

<Chemical foaming agent (B)>
The resin composition for a foam that can be used for producing a foam preferably contains a chemical foaming agent (B). The chemical foaming agent (B) is not particularly limited as long as the foam exhibits desired sound absorbing properties.
The chemical foaming agent (B) is not a heating type chemical foaming agent that requires heating for the foaming reaction, but foams by a chemical reaction with water, acid, base, etc. in a temperature range of -10 ° C or higher and 30 ° C or lower, for example. A non-pyrolytic chemical foaming agent that causes a reaction is preferred.
The base resin (A) may be deteriorated by heating, but by using such a non-pyrolytic chemical foaming agent, deterioration of the performance of the foam due to the deterioration of the base resin (A) can be suppressed. ..
In addition, the chemical foaming agent (B) preferably contains a dicarbonate diester (B-1) because it is easy to produce a foam exhibiting good sound absorbing properties. After preparing the resin composition for foam, the dicarbonate diester (B-1) is decomposed at a preferable rate according to the rate of the curing reaction of the base resin (A) even under low temperature conditions of about room temperature. Can foam. The dicarbonate diester (B-1) tends to foam better in the presence of water (C) than in anhydrous conditions.

For example, Japanese Patent Application Laid-Open No. 46-35992 states that when diethyl dicarbonate is added as a foaming agent to a foam resin composition in which unsaturated polyester is cured by an addition reaction, when a foam is produced at room temperature, It is disclosed that the expansion of the resin composition by foaming proceeds over a time of about 20 minutes, and the curing of the resin composition proceeds over a long time of more than 20 minutes (Japanese Patent Publication No. 46-35992). 8).
However, for example, when the base resin (A) having a reactive silicon group is foamed while being cured, the curing of the base resin (A) may proceed considerably in about 5 minutes. Therefore, if the chemical foaming agent (B) that foams over a period of as long as 20 minutes is applied to the resin composition for a foam containing the base resin (A) having a reactive silicon group, the desired foaming occurs. It is predicted that the base resin (A) will be rapidly cured before reaching the magnification, and only a foam having a low expansion ratio can be obtained.
However, as a result of examination by the present inventors, surprisingly, the resin composition for a foam containing the base resin (A) and the silanol condensation catalyst (D) contains the dicarbonate diester (B-1). It has been found that when the chemical foaming agent (B) is blended, the resin composition can be foamed to a desired degree in a short time.

The dicarbonate diester is represented by the following formula (B1).
R ^b- O-CO-O-CO-O-R ^b ... (B1)
In formula (B1), R ^b is an organic group. The organic group as R ^b is preferably a hydrocarbon group. The two R ^bs may be the same or different, and are preferably the same.

The number of carbon atoms of the hydrocarbon group as R ^b is preferably 1 or more and 16 or less, more preferably 1 or more and 12 or less, further preferably 1 or more and 8 or less, and particularly preferably 1 or more and 6 or less.
Examples of the hydrocarbon group as R ^b include an alicyclic group such as an alkyl group and a cycloalkyl group, an aralkyl group, and an aryl group. The alkyl group may be linear or branched, preferably linear.

Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group and n-hexyl group. Examples thereof include n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-undecyl group and n-dodecyl group.
Specific examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group and the like.
Specific examples of the aralkyl group include a benzyl group, a phenethyl group, a naphthalene-1-ylmethyl group, a naphthalene-2-ylmethyl group and the like.
Specific examples of the aryl group include phenyl, naphthalene-1-yl group, naphthalene-2-yl group, 4-phenylphenyl group, 3-phenylphenyl group, 2-phenylphenyl group and the like.

Examples of the dicarbonate diester (B-1) represented by the formula (B1) include dimethyl dicarbonate, diethyl dicarbonate, di-n-propyl dicarbonate, diisopropyl dicarbonate, di-n-butyl dicarbonate, and diisobutyl dicarbonate. , Di-sec-butyl dicarbonate, di-tert-butyl dicarbonate, di-n-pentyl dicarbonate, and di-n-hexyl dicarbonate are preferred. Dimethyl dicarbonate (B-1) includes dimethyl dicarbonate, diethyl dicarbonate, di-n-propyl dicarbonate, and dicarbonate because it is easily available and has a small molecular weight and a large amount of foaming per unit weight. Diisopropyl dicarbonate is preferred, and dimethyl dicarbonate and diethyl dicarbonate are more preferred. Further, from the viewpoint of high volatility and low toxicity of the product after the dicarbonate diester is hydrolyzed, diethyl dicarbonate is particularly preferable as the dicarbonate diester (B-1).

The resin composition for foams does not contain water (C) or may contain only a small amount of water (C), and achieves a high foaming ratio even when the amount of the chemical foaming agent (B) used is small. From the point of view of ease, it is also preferable that the chemical foaming agent (B) is mainly composed of dicarbonate diester (B-1).
The ratio of the weight of the dicarbonate diester (B-1) to the weight of the chemical foaming agent (B) is preferably 50% by weight or more, more preferably 70% by weight or more, further preferably 80% by weight or more, and 90% by weight. The above is particularly preferable, and 100% by weight or more is most preferable.

When the chemical foaming agent (B) contains a chemical foaming agent other than the dicarbonate diester (B-1), the other chemical foaming agents are known as various chemical foaming agents as long as the object of the present invention is not impaired. Agents can be used.
The dicarbonate (B-1) other than the preferred chemical blowing agent (B), tetraisocyanatesilane (Si _{(NCO) 4),} methyl triisocyanate silane _{_{(SiCH 3 (NCO) 3)}} , isocyanatomethyl-trimethoxysilane , Isocyanatomethyltriethoxysilane, 2-isocyanatoethyltrimethoxysilane, 2-isocyanatoethyltriethoxysilane, 3-isocyanato-n-propyltrimethoxysilane, 3-isocyanato-n-propyltriethoxysilane, 4- Examples thereof include isocyanate silane compounds (B-2) such as isocyanato-n-butyltrimethoxysilane and 4-isocyanato-n-butyltriethoxysilane. In particular, isocyanate silane having an alkoxysilyl group is preferable in that it is immobilized on the polymer.
The isocyanate silane compound (B-2) may be used in combination with the dicarbonate diester (B-1).

The amount of the chemical foaming agent (B) used can be appropriately selected in consideration of the foaming ratio of the foam.
The content of the chemical foaming agent (B) is preferably 2 parts by weight or more and 200 parts by weight or less, more preferably 5 parts by weight or more and 170 parts by weight or less, and 5 parts by weight or more with respect to 100 parts by weight of the base resin (A). It is more preferably 130 parts by weight or less, and particularly preferably 5 parts by weight or more and 100 parts by weight or less.

The content of the dicarbonate diester (B-1) as the chemical foaming agent (B) is preferably 1 part by weight or more and 50 parts by weight or less with respect to 100 parts by weight of the base resin (A), and is 2 parts by weight or more and 40 parts by weight. More preferably, it is 5 parts by weight or more and 30 parts by weight or less.

Although the chemical foaming agent (B) has been described above, in addition to foaming by the chemical foaming agent, a physical foaming agent may be added to the resin composition for foam to assist foaming. The boiling point of the physical foaming agent is preferably 100 ° C. or lower, more preferably 50 ° C. or lower, from the viewpoint of foamability, workability, and safety. Specific examples of the physical foaming agent include hydrocarbons (eg, LPG (propane), butane, etc.), halogenated hydrocarbons, ethers (eg, diethyl ethers), chlorofluorocarbons (CFCs), hydrofluorocarbons (HFCs), and hydrochloros. Examples thereof include fluorocarbons (HCFCs), fluoroolefins (FOs), chlorofluoroolefins (CFOs), hydrofluoroolefins (HFOs), hydrochlorofluorofluoroolefins (HCFOs), carbon dioxide, nitrogen, and air. Among these physical foaming agents, hydrocarbons, ethers, carbon dioxide, nitrogen, and air are preferable from the viewpoint of environmental compatibility.

<Water (C)>
The foam resin composition contains or does not contain water (C). Curing and foaming proceed even when the resin composition for foam does not contain water (C). On the other hand, water (C) has a function of accelerating the foaming reaction of the chemical foaming agent (B) and the curing reaction of the base resin (A).
When the resin composition for a foam contains water (C), the content of water (C) is preferably 1 part by weight or more and 70 parts by weight or less with respect to 100 parts by weight of the base resin (A), and 2 parts by weight. More than 60 parts by weight is more preferable, and 2 parts by weight or more and 50 parts by weight or less is further preferable. When the content of water (C) is within the above range, it is easy to proceed with curing satisfactorily while sufficiently foaming, and it is easy to obtain a foam having fine and dense foam cells and excellent flexibility.

When the foam resin composition contains dicarbonate diester (B-1) as the chemical foaming agent (B), the content of water (C) in the foam resin composition is the dicarbonate diester (B-1). It is preferably 0.05 parts by weight or more, and more preferably 0.1 parts by weight or more with respect to 1 part by weight. By using such an amount of water, the dicarbonate diester (B-1) can be satisfactorily reacted with water (B) to cause particularly good foaming, and the base resin (A) can be formed. The hydrolysis-condensation reaction between the reactive silicon groups has proceeded well.
In particular, when the foam resin composition contains only dicarbonate diester (B-1) as the chemical foaming agent (B), the content of water (C) in the foam resin composition is the dicarbonate diester (B-1). B-1) It is preferably 0.05 parts by weight or more and 0.5 parts by weight or less, and more preferably 0.05 parts by weight or more and 0.3 parts by weight or less with respect to 1 part by weight.
In this case, the content of water (C) in the foam after forming the foam can be reduced while causing particularly good foaming, and drying is performed to remove volatile components such as water during the production of the foam. The step can be omitted.
When the resin composition for a foam contains a dicarbonate diester (B-1) as a chemical foaming agent (B), the resin composition for a foam is only from the viewpoint of reducing the content of water (C) in the foam. The content of water (C) in the product is preferably 0 parts by weight or more and 0.05 parts by weight or less, and 0 parts by weight or more and 0.03 parts by weight with respect to 1 part by weight of the dicarbonate diester (B-1). It is more preferably parts by weight or less, and particularly preferably 0 parts by weight, that is, it does not contain water (C).
In addition, 1 mol of dicarbonate diester (B-1) reacts with 1 mol of water (C) to generate 2 mol of carbon dioxide gas (carbon dioxide). Therefore, from the viewpoint of efficiently foaming the dicarbonate diester (B-1) with water (C) in the resin composition for foam, the dicarbonate diester (B-1) and water (C) are used. The molar ratio of dicarbonate diester (B-1): water (C) is preferably 0.8: 1 to 1: 0.8, preferably 0.9: 1 to 1: 0.9. More preferably, it is 0.95: 1 to 1: 0.95.
The reason why foaming occurs well from the dicarbonate diester (B-1) even when water (C) is insufficient is unknown, but the water content of the dicarbonate diester (B-1) is added to the water in the air and in the material. It is considered that carbon dioxide is generated by decomposition or a decomposition reaction different from hydrolysis.

<Silanol condensation catalyst (D)>
The resin composition for a foam used in the production of the foam preferably contains a silanol condensation catalyst (D). The silanol condensation catalyst (D) is not particularly limited as long as it can be used as a condensation catalyst, and any one can be used. When the resin composition for a foam contains a dicarbonate diester (B-1) as a chemical foaming agent (B), the catalytic activity is lowered due to the influence of carbonic acid generated by the foaming reaction of the dicarbonate diester (B-1). A neutral or weakly acidic silanol condensation catalyst (D) is preferable because it is difficult. Carbonic acid is generated when carbon dioxide dissolves in water.

Examples of the silanol condensation catalyst (D) include tetravalent tin compounds, divalent tin compounds, and reactants and mixtures of the above-mentioned divalent tin compounds and amine-based compounds such as laurylamine described below. , Monoalkyltins, titanic acid esters, organic aluminum compounds, carboxylic acid metal salts, carboxylic acid metal salts and amine compounds such as laurylamine described below, chelate compounds, saturated aliphatic primary Amines, saturated aliphatic secondary amines, saturated aliphatic tertiary amines, aliphatic unsaturated amines, aromatic amines, other amines other than these amines, these amines and carboxylics. Salts with acids, etc., reactants and mixtures of amine compounds and organic tin compounds, low molecular weight polyamide resins obtained from excess polyamines and polybasic acids, reaction products of excess polyamines with epoxy compounds, amino groups Examples thereof include a silane coupling agent having an amino group, a modified derivative of a silane coupling agent having an amino group, and the like.

Examples of tetravalent tin compounds include dialkyltin dicarboxylates, dialkyltin alcoxides, intramolecular coordinating derivatives of dialkyltin, reactants of dialkyltin oxide and ester compounds, dialkyltin oxide and carboxylic acid. Examples thereof include a reaction product with an alcohol compound, a dialkyl compound, a reaction product between a dialkyl tin oxide and a silicate compound, and an oxy derivative (stanoxane compound) of these dialkyl tin compounds.

Specific examples of dialkyltin dicarboxylates include dibutyltin dilaurate, dibutyltin diacetate, dibutyltin di (2-ethylhexanoate), dibutyltin dioctate, dibutyltin diversate, dibutyltin distearate, and dibutyltin di (methyl). Maleate), Dibutyltin Di (Ethylmaleate), Dibutyltin Di (Butyl Maleate), Dibutyltin Di (Isooctyl Maleate), Dibutyltin Di (Tridecyl Maleate), Dibutyltin Di (Oleyl Maleate) , Dibutyltin di (benzylmaleate), dibutyltin maleate, dioctyltin diacetate, dioctyltin diversate, dioctyltin disteareate, dioctyltin dilaurate, dioctyltin di (ethylmaleate), dioctyltin di (isooctylmalate), etc. Can be mentioned.
The dibutyltin maleate is expressed by the following formula:
-Sn (-n-C ₄ H ₉ ) ₂ -OCO-CH = CH = COO-
It is an oligomer or polymer composed of a structural unit represented by.

Specific examples of dialkyltin alcoxysides include dibutyltin dimethoxyde and dibutyltin diphenoxide.

Specific examples of the intramolecular coordinating derivatives of dialkyltin include dibutyltin diacetylacetonate and dibutyltin diethylacetacetate.

Specific examples of the reaction product of the dialkyl tin oxide and the ester compound include a reaction product of a dialkyl tin oxide such as dibutyl tin oxide and dioctyl tin oxide and an ester compound such as dioctyl phthalate, diisodecyl phthalate and methyl maleate. ..

Examples of the reaction product of the dialkyltin oxide and the silicate compound include dibutyltin bistriethoxysilicate and dioctyltin bistriethoxysilicate.

Specific examples of the divalent tin compounds include tin octylate, tin naphthenate, tin stearate, tin ferzaticate and the like.

Specific examples of monoalkyl tins include monobutyl tin compounds such as monobutyl tin trisoctate and monobutyl tin triisopropoxide, and monooctyl tin compounds.

Specific examples of the titanic acid esters include tetrabutyl titanate, tetrapropyl titanate, tetra (2-ethylhexyl) titanate, isopropoxytitanium bis (ethylacetoacetate) and the like.

Specific examples of the organoaluminum compound include aluminum trisacetylacetonate, aluminumtrisethylacetate, di-isopropoxyaluminum ethylacetate and the like.

Specific examples of the metal carboxylate salt include bismuth carboxylate, iron carboxylate, titanium carboxylate, lead carboxylate, vanadium carboxylate, zirconium carboxylate, calcium carboxylate, potassium carboxylate, barium carboxylate, manganese carboxylate, Examples thereof include cerium carboxylate, nickel carboxylate, cobalt carboxylate, zinc carboxylate, aluminum carboxylate and the like. Specific examples of the carboxylic acid that gives the carboxylic acid metal salt include 2-ethylhexanoic acid, neodecanoic acid, versatic acid, oleic acid, and naphthenic acid.

Specific examples of the chelate compounds include zirconium tetraacetylacetonate, zirconium tributoxyacetylacetonate, dibutoxyzirconium diacetylacetonate, zirconium acetylacetonatebis (ethylacetacetone), titanium tetraacetylacetonate and the like.

Specific examples of saturated aliphatic primary amines include methylamine, ethylamine, propylamine, isopropylamine, butylamine, amylamine, hexylamine, octylamine, 2-ethylhexylamine, nonylamine, decylamine, laurylamine and pentadecylamine. , Cetylamine, stearylamine, cyclohexylamine and the like.

Specific examples of saturated aliphatic secondary amines include dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diamylamine, dioctylamine, di (2-ethylhexyl) amine, didecylamine, dilaurylamine, and disetylamine. Examples thereof include distearylamine, methylstearylamine, ethylstearylamine, butylstearylamine and the like.

Specific examples of saturated aliphatic tertiary amines include triamylamine, trihexylamine, trioctylamine, 1,4-diazabicyclo [2.2.2] octane (DABCO) and the like.

Specific examples of aliphatic unsaturated amines include triallylamine, oleylamine and the like.

Specific examples of aromatic amines include laurylaniline, stearylaniline, triphenylamine and the like.

Specific examples of amines other than the above amines include monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, benzylamine, diethylaminopropylamine, xylylenediamine, ethylenediamine, hexamethylenediamine. , Triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris (dimethylaminomethyl) phenol, morpholin, N-methylmorpholin, 2-ethyl-4-methylimidazole, 1,8-diazabicyclo [5.4.0] ] -7-Amine-based compounds such as undecene (DBU) can be mentioned.

Examples of the reaction product and mixture of the amine compound and the organic tin compound include a reaction product or a mixture of laurylamine and tin octylate.

Specific examples of the silane coupling agent having an amino group include 3-amino-n-propyltrimethoxysilane, 3-amino-n-propyltriethoxysilane, 3-amino-n-propyltriisopropoxysilane, and 3-. Amino-n-propylmethyldimethoxysilane, 3-amino-n-propylmethyldiethoxysilane, N- (β-aminoethyl) -3-amino-n-propyltrimethoxysilane, N- (β-aminoethyl)- 3-Amino-n-propylmethyldimethoxysilane, N- (β-aminoethyl) -3-amino-n-propyltriethoxysilane, N- (β-aminoethyl) -3-amino-n-propylmethyldiethoxy Silane, N- (β-aminoethyl) -3-amino-n-propyltriisopropoxysilane, 3-ureido-n-propyltrimethoxysilane, N-phenyl-3-amino-n-propyltrimethoxysilane, N Examples thereof include -benzyl-3-amino-n-propyltrimethoxysilane and N-vinylbenzyl-3-amino-n-propyltriethoxysilane.

Examples of the derivative obtained by modifying the above-mentioned silane coupling agent having an amino group include an amino-modified silyl polymer, a silylated amino polymer, an unsaturated amino silane complex, a phenylamino long chain alkyl silane, and an amino silylated silicone.

Further, fatty acids such as ferzatic acid, other acidic catalysts such as organic acidic phosphoric acid ester compounds, basic catalysts and the like can be exemplified as known silanol condensation catalysts.

Examples of the organic acidic phosphoric acid ester compound of the acidic catalyst include (CH ₃ O) _2- P (= O) (-OH), (CH ₃ O) -P (= O) (-OH) ₂ , (C ₂ H). ₅ O) _2- P (= O) (-OH), (C ₂ H ₅ O) -P (= O) (-OH) ₂ , (C ₃ H ₇ O) _2- P (= O) (- OH), (C ₃ H ₇ O) -P (= O) (-OH) ₂ , (C ₄ H ₉ O) _2- P (= O) (-OH), (C ₄ H ₉ O) -P (= O) (-OH) ₂ , (C ₈ H ₁₇ O) _2- P (= O) (-OH), (C ₈ H ₁₇ O) -P (= O) (-OH) ₂ , (C ₁₀ H ₂₁ O) _2- P (= O) (-OH), (C ₁₀ H ₂₁ O) -P (= O) (-OH) ₂ , (C ₁₃ H ₂₇ O) _2- P (= O) (-OH), (C ₁₃ H ₂₇ O) -P (= O) (-OH) ₂ , (C ₁₆ H ₃₃ O) _2- P (= O) (-OH), (C ₁₆ H ₃₃ O) -P (= O) (-OH) ₂ , (HO-C ₆ H ₁₂ O) _2- P (= O) (-OH), (HO-C ₆ H ₁₂ O) -P (= O) (- _{_{_{OH) 2, (HO-C}}} 8 H 16 O) -P (= O) (- OH), (HO-C 8 H 16 O) -P (= O) (- OH) 2, [(CH 2 OH ) (CHOH) O] _2- P (= O) (-OH), [(CH ₂ OH) (CHOH) O] -P (= O) (-OH) ₂ , [(CH ₂ OH) (CHOH) C ₂ H ₄ O] _2- P (= O) (-OH), [(CH ₂ OH) (CHOH) C ₂ H ₄ O] -P (= O) (-OH) _2, etc. It is not limited to the exemplary substance.

From the viewpoint of satisfactorily curing the resin composition for foam, among the preferred examples of the silanol condensation catalyst (D) described above, a tin-containing catalyst containing Sn is preferable, and dialkyltin dicarboxylates and dialkyltin. Alcoxides, intramolecular coordinating derivatives of dialkyl tin, reaction products of dialkyl tin oxide and ester compounds, tin compounds obtained by reacting dialkyl tin oxide, carboxylic acids and alcohol compounds, dialkyl tin oxide and silicate compounds , And tetravalent tin compounds such as oxy derivatives (stanoxane compounds) of these dialkyl tin compounds are preferably contained.
As the tin-containing catalyst, the higher the ratio of the mass of tin atoms to the mass, the higher the catalytic activity, which is preferable.
Further, from the viewpoint of suppressing shrinkage of the foam over time after the production of the foam, dialkyltin dicarboxylates are preferable as the silanol condensation catalyst (D), and dibutyltin diacetate is more preferable.

The catalytic activity is unlikely to decrease due to the influence of carbon dioxide generated by the foaming reaction of the dicarbonate diester (B-1), and the foaming reaction between the dicarbonate diester (B-1) and water and the curing of the base resin (A) Among the silanol condensation catalysts (D) listed above, a neutral or weakly acidic silanol condensation catalyst is preferable, and a weakly acidic silanol condensation catalyst is more preferable, from the viewpoint of allowing the reaction to proceed in a particularly well-balanced manner. Carbonic acid is generated when carbon dioxide dissolves in water.
Further, when a neutral or weakly acidic silanol condensation catalyst is used, it is difficult to inhibit the progress of the foaming reaction of the dicarbonate diester (B-1) with water at the start of foaming.
The silanol condensation catalyst (D) is a neutral or weakly acidic catalyst among the various tin-containing catalysts described above as a neutral or weakly acidic silanol condensation catalyst because the base resin (A) can be easily cured. Is preferably included.
From this point of view, dialkyltin dicarboxylates are preferable as the neutral or weakly acidic tin-containing catalyst with respect to the silanol condensation catalyst (D).
As the neutral or weakly acidic dialkyltin dicarboxylate, a compound represented by the following formula (D1) or an oligomer or polymer composed of a structural unit represented by the following formula (D2) is preferable.
(R ^d1 ) (R ^d2 ) (R ^d3 COO) (R ^d4 COO) Sn ... (D1)
-(-(R ^d1 ) (R ^d2 ) Sn-OCOR ^d5 COO-)-... (D2)
In formulas (D1) and (D2), R ^d1 and R ^d2 may be the same or different, respectively. R ^d1 and R ^d2 are linear or branched alkyl groups, and a linear alkyl group is preferable. The number of carbon atoms of the alkyl group as R ^d1 and R ^d2 is not particularly limited, and is preferably 1 or more and 20 or less, more preferably 2 or more and 16 or less, and further preferably 3 or more and 10 or less. Since the tin-containing catalyst is easily available and the activity of the tin-containing catalyst as a silanol condensation catalyst (D) is good, n-butyl group and n-octyl group are used as R ^d1 and R ^d2. preferable.
In the formula (D1), R ^d3 and R ^d4 are organic groups having 1 or more and 40 or less carbon atoms, respectively. The number of carbon atoms of the organic group as R ^d3 and R ^d4 is preferably 1 or more and 30 or less. The organic groups as R ^d3 and R ^d4 may contain heteroatoms such as O, S, N, and Si.
Since the tin-containing catalyst is easily available and the activity of the tin-containing catalyst as a silanol condensation catalyst (D) is good, the R ^d3 and R ^d4 are linear with 1 to 30 carbon atoms. Alternatively, a branched alkyl group and the following formula (D3):
-CH = CH-CO-OR ^d6 ... (D3)
The group represented by is preferable. R ^d6 is a hydrocarbon group having 1 or more and 30 or less carbon atoms. The hydrocarbon group may be an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a combination of an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The number of carbon atoms of the hydrocarbon group as R ^d6 is preferably 1 or more and 20 or less.
In the formula (D2), R ^d5 is a divalent organic group having 1 or more and 40 or less carbon atoms. The number of carbon atoms of the organic group as R ^d5 is preferably 1 or more and 30 or less, more preferably 1 or more and 10 or less, and further preferably 1 or more and 4 or less. The organic group as R ^d5 may contain heteroatoms such as O, S, N, and Si. As the organic group as R ^d5 , a hydrocarbon group is preferable, and -CH = CH- and -CH ₂ CH ₂ --are more preferable.
Preferable specific examples of the compound represented by the above formula (D1) or the oligomer or polymer composed of the structural unit represented by the above formula (D2) are as described above as specific examples of dialkyltin dicarboxylates. , Dibutyltin diacetate is particularly preferred.
Whether the silanol condensation catalyst is neutral or weakly acidic can be determined by measuring the pH of a 1% by mass water / acetone = 10/90 (weight ratio) solution of the silanol condensation catalyst at 20 ° C. it can. Specifically, when the pH is 6.5 or more and less than 7.5, it is neutral, and when the pH is 4.0 or more and less than 6.5, it is weakly acidic.
When a resin composition for a foam containing a neutral or weakly acidic silanol condensation catalyst (D) is used, foaming and the effect can be easily promoted in a short time. Therefore, the resin composition for a foam containing a neutral or weakly acidic silanol condensation catalyst (D) is particularly useful when constructing a foam at a construction site or a manufacturing site of various industrial products. Is.
This is because foaming and curing in a short time are required for the construction of the foam on site.

Preferable examples of the basic silanol condensation catalyst (D) are the above-mentioned aliphatic primary amines, aliphatic secondary amines, aliphatic tertiary amines, and aliphatic unsaturated amines, respectively. , And aromatic amines, other amines other than these amines, and silane coupling agents having an amino group.
When the above amines or a silane coupling agent having an amino group is used alone as a silanol condensation catalyst, the curing reaction of the base resin (A) may be slightly slow. Therefore, the above-mentioned amines and the silane coupling agent having an amino group are used in combination with a catalyst having a high effect of accelerating the curing reaction of the base resin (A), such as the above-mentioned various tin-containing catalysts. preferable.
In particular, the basic silanol condensation catalyst (D) is preferably used in combination with a neutral or weakly acidic tin-containing catalyst, more preferably in combination with dialkyltin dicarboxylates, and dibutyltin dicarboxylate. Is most preferred.

The content of the silanol condensation catalyst (D) is preferably 90 parts by weight or less, more preferably 0.05 parts by weight or more and 80 parts by weight or less, and 0.05 parts by weight or more with respect to 100 parts by weight of the base resin (A). 20 parts by weight or less is more preferable, and 1 part by weight or more and 15 parts by weight or less is even more preferable. If the content of the silanol condensation catalyst (D) is more than 80 parts by weight, the foam may bottom out due to compression of the obtained foam. By adjusting the amount of the silanol condensation catalyst (D), the curability of the foam resin composition can be adjusted.

<Effervescent aid (E)>
When the resin composition for a foam contains a dicarbonate diester (B-1) as a chemical foaming agent (B), the resin composition for a foam is a foaming aid (E) and / or a foaming aid (E). It is preferable to include a silanol condensation catalyst (D) that acts as a resin.
The foaming aid (E) is a component that promotes foaming due to the decomposition of the dicarbonate diester (B-1). The foaming aid (E) is not particularly limited as long as it is a compound that promotes foaming when added to a mixture containing water and a dicarbonate diester (B-1).

Typically, the foaming aid (E) preferably includes an organic or inorganic basic compound. Therefore, the basic catalyst described above as the silanol condensation catalyst may act as a foaming aid (E).
For example, when the resin composition for a foam contains a component that acts as a foaming aid (E) such as the above-mentioned basic silanol condensation catalyst as the silanol condensation catalyst (D), foaming is conveniently performed. The body resin composition is treated as containing both the silanol condensation catalyst (D) and the foaming aid (E).

Preferable examples of the silanol condensation catalyst (D) acting as a foaming aid (E) are bis (N, N-dimethylamino-2-ethyl) ether, triethylenediamine and N, N, N', N'-. Tetramethylhexamethylenediamine, N-ethylmorpholin, tetramethylethylenediamine, diaminobicyclooctane, 1,2-dimethylimidazole, 1-methylimidazole and 1,8-diazabicyclo- [5.4.0] -7-undecene (DBU) ), 1,4-diazabicyclo [2.2.2] Octane (DABCO) and other tertiary amines that do not contain active hydrogen, and hydroxyl and thiol groups such as dimethylethanolamine, diethylethanolamine and dimethylhexanolamine. , Tertiary amine containing active hydrogen having an active hydrogen-containing group such as a carboxy group.

The content of the foaming aid (E) that does not correspond to the silanol condensation catalyst (D) is preferably 0.05 parts by weight or more and 20 parts by weight or less, preferably 0.1 parts by weight, based on 100 parts by weight of the base resin (A). More than 10 parts by weight is more preferable, and 0.5 parts by weight or more and 5 parts by weight or less is further preferable.
The content of the silanol condensation catalyst (D) acting as the foaming aid (E) is the same as the content of the silanol condensation catalyst (D) described above.

<Other additives>
A plasticizer, a reactivity modifier, and a dye can be added to the foam resin composition for the purpose of adjusting the flexibility and molding processability of the foam.

As the plasticizer, a plasticizer having a main chain composed of repeating units composed of oxyalkylene-based units is preferable. Specific examples of the main chain include polyethylene oxide, polypropylene oxide, polybutylene oxide; two or more random or block copolymers selected from ethylene oxide, propylene oxide, and butylene oxide, which are used alone. Alternatively, two or more types may be used in combination. Of these, polypropylene oxide is preferable in terms of compatibility with the base resin (A). Further, those obtained by modifying these oxyalkylenes with isocyanate can also be added.

The molecular weight of the plasticizer has a number average molecular weight of 1000 or more, preferably 3000 or more, from the viewpoint of the flexibility of the obtained foam and the prevention of the plasticizer from flowing out of the system. When the number average molecular weight is within the above range, it is possible to suppress the outflow of the plasticizer from the system over time due to heat, compression, etc., it is easy to maintain the initial physical properties for a long period of time, and there is little adverse effect on flexibility. .. The upper limit is not particularly limited, but if the number average molecular weight becomes too high, the viscosity increases and workability deteriorates. Therefore, 50,000 or less is preferable, and 30,000 or less is more preferable. The plasticizer is not particularly limited as long as it can impart flexibility to the foam, and may be linear or branched.

The amount of the plasticizer added is preferably 5 parts by weight or more and 150 parts by weight or less, more preferably 10 parts by weight or more and 120 parts by weight or less, and further preferably 20 parts by weight with respect to 100 parts by weight of the base resin (A). It is 100 parts by weight or less. When the amount of the plasticizer added is within the above range, it is easy to adjust the flexibility and moldability, have good mechanical strength, and easily form a foam having a desired foaming ratio. The method for producing the plasticizer is not particularly limited, and a known production method can be applied, and a commercially available compound may be used.

The reactivity modifier preferably has a reactive silicon group. The reactivity modifier may be a silicate compound such as methyl silicate or ethyl silicate, a copolymer of a vinyl monomer having a reactive silicon group, or a reactive silicon having a chain transfer group such as thiol. It may be a copolymer using a monomer. These may be used alone or in combination of two or more.

The molecular weight of the reactivity modifier is preferably 1000 or more, more preferably 3000 or more, in terms of number average molecular weight from the viewpoint of curing and foaming of the obtained foam. The upper limit is not particularly limited, but is preferably 50,000 or less, more preferably 30,000 or less, because the viscosity of the resin composition for foam can be easily set within a workable range. The reactivity modifier is not particularly limited as long as it can adjust the curability of the foam resin composition, whether it is linear or branched.

The amount of the reactivity adjusting agent added is preferably 2 parts by weight or more and 120 parts by weight or less, more preferably 5 parts by weight or more and 80 parts by weight or less, and further preferably 10 parts by weight with respect to 100 parts by weight of the base resin (A). It is 50 parts by weight or more and 50 parts by weight or less. When an amount of the reaction modifier within such a range is used, the curability can be easily adjusted within an appropriate range, and curing can proceed at an appropriate rate to easily obtain a foam having a high foaming ratio. The method for producing the reactivity adjusting agent is not particularly limited, and a known production method can be applied, and a commercially available compound may be used.

A light resistance stabilizer, an ultraviolet absorber, a storage stabilizer, a bubble modifier, a lubricant, a flame retardant, etc. may be added to the foam resin composition as necessary, as long as the effects of the present invention are not impaired. Good.

Examples of the light resistance stabilizer include a hindered phenol-based antioxidant and a hindered amine-based light stabilizer containing no sulfur atom, phosphorus atom, primary amine, or secondary amine. Here, the light resistance stabilizer has a function of absorbing light having a wavelength in the ultraviolet region to suppress the generation of radicals, or a function of capturing radicals generated by light absorption and converting them into thermal energy to make them harmless. It is a compound that enhances the stability against light.

The ultraviolet absorber is not particularly limited, and examples thereof include a benzoxazine-based ultraviolet absorber, a benzophenone-based ultraviolet absorber, a benzotriazole-based ultraviolet absorber, and a triazine-based ultraviolet absorber. Here, the ultraviolet absorber is a compound having a function of absorbing light having a wavelength in the ultraviolet region and suppressing the generation of radicals.

The amount of the light-resistant stabilizer and the ultraviolet absorber added is preferably 0.01 parts by weight or more and 5 parts by weight or less, and 0.1 parts by weight or more and 3 parts by weight or more, respectively, with respect to 100 parts by weight of the base resin (A). More preferably, it is 0.3 parts by weight or more, and further preferably 2.0 parts by weight or less. When the amount of the light-resistant stabilizer and the ultraviolet absorber added is within the above range, the effect of suppressing an increase in surface adhesiveness with time can be easily obtained.

Preferred examples of the storage stability improving agent include, for example, a compound containing an aliphatic unsaturated bond, an organic phosphorus compound, an organic sulfur compound, a nitrogen-containing compound, a tin compound, and an organic peroxide. These may be used alone or in combination of two or more. Specifically, 2-benzothiazolyl sulfate, benzothiazole, thiazole, dimethylacetylene dicarboxylate, diethylacetylene dicarboxylate, 2,6-di-t-butyl-4-methylphenol, butylhydroxyanisole, vitamins. E, 2- (4-morphozynyldithio) benzothiazole, 3-methyl-1-buten-3-ol, acetylene unsaturated group-containing organosiloxane, acetylene alcohol, 3-methyl-1-butyne-3-ol , 2-Methyl-3-butyne-2-ol, diallyl fumarate, diallyl maleate, diethyl fumarate, diethyl maleate, dimethyl maleate, 2-pentenenitrile, 2,3-dichloropropene and the like.

If necessary, a bubble modifier may be added to the foam resin composition. The type of the bubble adjusting agent is not particularly limited, and examples thereof include inorganic solid powders usually used, such as talc, magnesium oxide, titanium oxide, zinc oxide, carbon black, and silica. These may be used alone or in combination of two or more.

Since it is easy to produce a foam that satisfactorily absorbs sound components having a frequency of 1000 Hz or less or 800 Hz or less, the content of metal salts and / or inorganic particles in the foam is 2 with respect to the weight of the foam. It is preferably 5.5% by weight or less, and more preferably 1% by weight or less. The metal salt may be an inorganic salt or an organic salt containing an organic anion or an organic cation.
Therefore, when the resin composition for a foam contains an inorganic solid powder, the amount of the inorganic solid powder used is preferably adjusted so that the amount of the inorganic solid powder used in the foam is the above amount. ..

The amount of the bubble adjusting agent used is preferably 0.1 part by weight or more and 100 parts by weight or less, and more preferably 0.5 parts by weight or more and 50 parts by weight or less with respect to 100 parts by weight of the base resin (A).

If necessary, a foam stabilizer may be added to the resin composition for foam. The type of the foam stabilizer is not particularly limited, and examples thereof include silicone oil-based compounds such as polyether-modified silicone oil and fluorine-based compounds, which are usually used. These may be used alone or in combination of two or more. In particular, polypropylene and polyethylene-modified silicone may be expected to have foam-regulating power in a small amount.

The amount of the foam stabilizer used is preferably 0.2 parts by weight or more and 30 parts by weight or less, and more preferably 0.5 parts by weight or more and 15 parts by weight or less with respect to 100 parts by weight of the base resin (A).

Hollow particles may be added to the resin composition for foam, if necessary. The type of hollow particles is not particularly limited, and is generally used, for example, a thermoplastic shell polymer containing a volatile liquid that becomes gaseous at a temperature below the softening point of the shell polymer and heated to volatilize. Examples thereof include those in which the sex liquid becomes gaseous and the shell polymer is softened and expanded. It is also possible to add hollow particles before expansion and foam them during molding.

The amount of the hollow particles used is preferably 0.2 parts by weight or more and 30 parts by weight or less, and more preferably 0.5 parts by weight or more and 15 parts by weight or less with respect to 100 parts by weight of the base resin (A).
When the hollow particles are inorganic particles such as hollow silica and glass balloon, the preferable amount to be used is the same as the preferable amount to be used for the inorganic solid powder.

Further, a lubricant can be added for the purpose of improving the compatibility of the components contained in the resin composition for foam.

By containing a lubricant, friction and adhesion in the foam cell of the foam formed by foaming the resin composition for foam can be reduced, and a foam having desired flexibility can be obtained. Further, the lubricant is held by the three-dimensional network structure formed by the silanol condensation reaction between the base resins (A), and tends to suppress bleeding out of the foam system, so that it is flexible for a long period of time. It becomes possible to maintain sex.

As the lubricant, a liquid lubricant is preferable. Specific examples of liquid lubricants include animal and vegetable oils such as paraffin mineral oil, naphthenic mineral oil, and fatty acid glyceride; olefin lubricants having an alkyl structure such as poly-1-decene and polybutene; alkyl aromatics having an aralkyl structure. Compound-based lubricants; Polyalkylene glycol-based lubricants; Ether-based lubricants such as polyalkylene glycol ethers, perfluoropolyethers, and polyphenyl ethers; fatty acid esters, fatty acid diesters, polyol esters, silicic acid esters, phosphoric acid esters, etc. Ester-based lubricants with an ester structure; dimethyl silicone (ie, dimethylpolysiloxane with both terminal trimethylsiloxy groups blocked), and some of the methyl groups of dimethylsilicone are polyether groups, phenyl groups, alkyl groups, aralkyl groups, and fluorinated Examples thereof include silicone-based lubricants such as silicone oil substituted with an alkyl group and the like; fluorine atom-containing lubricants such as chlorofluorocarbon. These may be used alone or in combination of two or more.

Among these lubricants, silicone-based lubricants are particularly preferable from the viewpoint of reducing the coefficient of friction in the foam cell, dispersibility, workability, safety, and the like.

The amount of the lubricant added is preferably 1 part by weight or more, more preferably 2 parts by weight or more, and further preferably 3 parts by weight or more with respect to 100 parts by weight of the base resin (A). The upper limit of the amount of the lubricant added is not particularly limited, but is preferably 25 parts by weight or less, more preferably 20 parts by weight or less. When an amount of lubricant within such a range is used, friction and adhesion in the foam cell can be easily suppressed, the foaming ratio can be easily increased, bleeding out of the lubricant to the outside of the system can be easily suppressed, and foaming with desired flexibility can be easily performed. Easy to get a body.

Preferable specific examples of the flame retardant include red phosphorus, phosphoric acid ester, phosphate-containing flame retardant, bromine-containing flame retardant, boron-containing flame retardant, antimony-containing flame retardant, and metal hydroxide. These may be used alone or in combination of two or more. As the flame retardant, red phosphorus is used in combination with at least one selected from phosphoric acid ester, phosphate-containing flame retardant, bromine-containing flame retardant, boron-containing flame retardant, antimony-containing flame retardant, and metal hydroxide. It is preferable to be done.

Since foaming easily proceeds in an environment where the chemical foaming agent (B) and water (C) coexist, the resin composition for a foam is used as a two-component or three-component or more liquid type liquid composition. May occur. Since it is easy to prepare the resin composition for foam by mixing, the resin composition for foam is preferably a two-component resin composition.

The multi-component resin composition contains a first liquid containing a base resin (A), a chemical foaming agent (B) such as dicarbonate diester (B-1), and at least a silanol condensation catalyst (D). It is preferable to contain two liquids.
It is also preferable that the second liquid contains water (C). When the silanol condensation catalyst (D) is contained in the first liquid, curing due to cross-linking between the base resin (A) may proceed. However, by containing the silanol condensation catalyst (D) in a liquid different from the first liquid, it is possible to prevent the base resin (A) from being cured before the foam is produced. When the second liquid contains a silanol condensation catalyst (D), the silanol condensation catalyst (D) preferably contains a neutral or weakly acidic silanol condensation catalyst, and more preferably contains a weakly acidic silanol condensation catalyst.

Further, in the multi-component resin composition, the foaming aid (E) and / or the foaming aid (E) are added to the second liquid containing the silanol condensation catalyst (D) or the liquids other than the first liquid and the second liquid. ), It is preferable to contain a silanol condensation catalyst (D), or a foaming aid (E) and water (C).

≪Manufacturing method of foam≫
The method for producing the foam is not particularly limited. When the above-mentioned resin composition for foam is used, the method for producing the foam is, for example, a batch method in which the resin composition for foam is filled in a mold, and then foamed and cured in the mold. Alternatively, it may be a continuous type in which the resin composition for a foam is continuously foamed and cured on a continuously moving band-shaped support. A non-woven fabric can be used as the support.

Further, the above-mentioned resin composition for a foam is completely liquid or a pigment (for example, carbon black) or the like by using a dicarbonate diester (B-1) as the chemical foaming agent (B). It can be a low-viscosity composition containing only a small amount of insoluble matter. Further, the foam resin composition containing dicarbonate diester (B-1) does not necessarily have to contain a component that is difficult to dissolve in the foam resin composition such as carbonate or bicarbonate.
When the resin composition for foam has a low viscosity, a one-component, two-component or more multi-component resin composition for foam is discharged onto the construction surface and collided and mixed on the construction surface. It is possible to form a film-like foam on the construction surface.

The foam is typically a first liquid containing a base resin (A) having a reactive silicon group, a chemical foaming agent (B) such as dicarbonate diester (B-1), and a silanol condensation catalyst ( It is produced by a method including a mixing step of mixing with D) to obtain a mixed solution.
In this method, in the mixed solution, the foaming rate due to the decomposition of the chemical foaming agent (B) such as dicarbonate diester (B-1) and the curing reaction rate of the mixed solution due to the reaction between the reactive silicon groups are desired. It is preferable to adjust each of them so as to obtain a foam having a foaming ratio of the same. The desired foaming ratio is, for example, 2 times or more and 60 times or less.

The foaming rate due to the decomposition of the chemical foaming agent (B) such as dicarbonate diester (B-1) is determined by, for example, the type and amount of the chemical foaming agent (B), the content of water (C) in the mixed solution, and foaming. By appropriately changing the temperature of the environment in which the body is produced, the type and content of the foaming aid (E) and / or the silanol condensation catalyst (D) acting as the foaming aid (E) in the mixed solution, and the like. Can be adjusted.
The rate of curing reaction of the mixed solution is, for example, the type and amount of reactive silicon contained in the base resin (A), the type and content of the silanol condensation catalyst (D) in the mixed solution, and the water in the mixed solution ( It can be adjusted by appropriately changing the content of C), the temperature of the environment in which the foam is produced, and the like.
The foaming rate due to the decomposition of the chemical foaming agent (B) and the curing reaction rate of the mixed solution are preferably adjusted so that the foaming ratio of the obtained foam is 2 times or more and 60 or less, and the foaming ratio is high. It is more preferable that the adjustment is made so as to be 5 times or more and 40 times or less.

The amount of the chemical foaming agent (B) used and the amount of the silanol condensation catalyst (D) used in the above production method are as described above for the composition.

In the above mixing step, it is preferable that the silanol condensation catalyst (D) acting as the foaming aid (E) and / or the foaming aid (E) is mixed with the first liquid. As the silanol condensation catalyst (D) acting as a foaming aid (E), 1,4-diazabicyclo [2.2.2] octane is preferable.

The temperature at which the resin composition for a foam is cured and foamed is not particularly limited. The temperature at which the resin composition for a foam is cured and foamed is, for example, preferably −10 ° C. or higher and 40 ° C. or lower, and more preferably 0 ° C. or higher and 37 ° C. or lower. Under such temperature conditions, it is easy to produce a foam using the resin composition for foam at the site where the foam is used.
There is no particular limitation on the time required for curing and foaming to complete. For example, 12 minutes or less is preferable, and 10 minutes or less is more preferable.

The foam produced in this manner is preferably distributed and sold as a foam product after being dried.
The conditions of the drying temperature and time are not particularly limited as long as they can be derived from the resin composition for foam or the water, alcohol, etc. produced by the curing reaction can be reduced to a desired degree. The drying conditions may be, for example, about 1 hour in an atmosphere of about 80 ° C. The drying temperature and time conditions may be, for example, about 12 hours in an atmosphere of about 60 ° C.
However, as described above, when only the dicarbonate diester (B-1) is used as the chemical foaming agent (B) and the amount of water (C) used is set low, the product can be produced without drying. Is.

≪Sound absorbing material≫
The sound absorbing material includes the above-mentioned foam. The sound absorbing material may be composed of only a foam, or may be composed of a foam and a member other than the foam. For example, a composite in which a foam is fixed to a support such as a metal plate, a wooden plate, a plastic sheet, corrugated cardboard, or cardboard can be used as a sound absorbing material.

≪Use of sound absorbing material≫
Since the above sound absorbing material includes the above-mentioned foam, it exhibits good sound absorbing characteristics. Therefore, the above-mentioned sound absorbing material can be suitably used for manufacturing various articles to which various sound absorbing materials have been conventionally applied.
As described above, the above-mentioned sound absorbing material can satisfactorily absorb noise in daily life. Therefore, a building provided with the above-mentioned sound absorbing material and a vehicle provided with the above-mentioned sound absorbing material are preferable as articles provided with the sound absorbing material.

Further, the sound absorbing material is also preferably used as a sound absorbing material for pneumatic tires. The noise in automobiles is mainly tire pattern noise, which is 800 Hz or less.
As will be described in more detail with reference to the examples and drawings, the sound absorbing material described above exhibits better sound absorbing properties in the frequency range below 800 Hz than well known foams such as polyurethane foam.

The method of attaching the above-mentioned sound absorbing material to the pneumatic tire is not particularly limited. The sound absorbing material is preferably provided, for example, in the cavity of the pneumatic tire as a band-shaped member extending in the tire circumferential direction. The shape of the band-shaped member may be an arc shape or an annular shape, and an annular shape is preferable.

The strip-shaped member may be arranged at a position away from the inner surface of the pneumatic tire, may be arranged in contact with the inner surface of the pneumatic tire, and is preferably arranged in contact with the inner surface of the pneumatic tire. Further, the band-shaped member made of the sound absorbing material is preferably fixed in contact with the inner surface of the pneumatic tire by using an adhesive or a fixing tool such as a screw.

The size of the band-shaped member is preferably a size in which the volume of the band-shaped member is 0.1% or more and 30% or more, and 0.5% or more and 20% or less of the volume of the cavity of the pneumatic tire. Is more preferable.

The shape of the cross section of the strip-shaped member perpendicular to the tangential direction in the tire circumferential direction is not particularly limited. Preferred examples of such cross-sectional shapes include squares, rectangles, triangles (preferably isosceles triangles), trapezoids, and semicircles, and shapes that roughly approximate these shapes.
Further, the shape of the cross section is such that the inner surface side of the pneumatic tire is smooth, and one or more protrusions (the surface on the rotation center side of the pneumatic tire) opposite to the inner surface side surface of the pneumatic tire. A shape having 2 or 3 protrusions) is preferable.

≪Sound absorption method≫
As described above, the above foam has a sound absorption coefficient of 70 at a frequency of 1000 Hz to 5500 Hz, which is measured using a B tube at 20 ° C. using a sample having a thickness of 25 mm and in accordance with JIS A 1405-2. % Or more.
Therefore, various sounds, particularly noise, can be absorbed by using the foam or the sound absorbing material described above. Since the above-mentioned foam or sound absorbing material can absorb sound in a wide frequency band, it is preferable to use the above-mentioned foam or sound absorbing material to absorb sound containing components in the frequency range of 1000 Hz to 5500 Hz.

The above foam has a maximum sound absorption coefficient in the frequency range of 1000 Hz to 1700 Hz measured using a B tube at 20 ° C. in accordance with JIS A 1405-2 using a sample having a thickness of 25 mm. Is preferable.
Further, the above foam has a sound absorption coefficient of 40% or more at a frequency of 800 Hz, which is measured using a B tube at 20 ° C. using a sample having a thickness of 25 mm and in accordance with JIS A 1405-2. Is preferable.
Further, the above foam has a sound absorption coefficient of 90% or more at a frequency of 1500 Hz, which is measured using a B tube at 20 ° C. using a sample having a thickness of 25 mm and in accordance with JIS A 1405-2. Is preferable.

The foam absorbs well the components in the frequency range of 1000 Hz to 5500 Hz, and particularly well absorbs the components in the frequency range of 1000 Hz to 1700 Hz among the sounds to be absorbed.
As described above, the sounds including the components in the frequency range of 1000 Hz to 1700 Hz include daily conversation, musical instrument sounds such as a piano and a clarinet. Therefore, the above-mentioned foam tends to absorb noise that is particularly annoying in daily life.
Therefore, the above-mentioned foam or sound absorbing material is preferably used in daily conversation or in a method of causing the foam or sound absorbing material to absorb noise containing components in the frequency range of 1000 Hz to 1700 Hz derived from musical instrument sounds. ..

Further, the above-mentioned foam or sound absorbing material is preferably used in a method of causing the foam or sound absorbing material to absorb noise of 800 Hz or less, which is called tire pattern noise.

≪Other sound absorbing materials≫
As another preferable sound absorbing material (also referred to as “another sound absorbing material” in the present specification), a sound absorbing material made of a foam material satisfying the following specific physical properties can be mentioned. Foam as the material of the other sound absorbing material, the foam, the less shear modulus 7000 Pa, not particularly limited so long as they exhibit the flow resistance per 1000000N · s / m ⁴ or more unit thickness.
The foam showing the shear modulus and the flow resistance per unit thickness exhibits good sound absorption characteristics in a wide frequency band including a low frequency band of 1000 Hz or less and a high frequency band of more than 2000 Hz.

The shear modulus of the foam as another sound absorbing material is preferably 6000 Pa or less, and more preferably 5000 Pa or less.
Further, the lower limit of the shear elastic modulus of the foam as another sound absorbing material is not particularly limited. The shear modulus of the foam as another sound absorbing material is preferably 500 Pa or more, more preferably 1000 Pa or more, and even more preferably 2000 Pa or more.
Other foams as sound absorbing materials may have a skin layer. Conventionally known sound absorbing materials made of foam often do not exhibit the desired sound absorbing performance when they have a skin layer, and are used in a state where the skin layer is cut off. However, in a foam having a shear modulus of 7,000 Pa or less, which is soft, excellent sound absorption can be exhibited regardless of the presence or absence of a skin layer.

Flow resistance per unit thickness of the foam as another sound-absorbing material, preferably 1500000N · s / ^{m 4} or more, 2000000N · s / ^{m 4} or more is more preferable.
Further, the lower limit of the flow resistance per unit thickness of the foam as another sound absorbing material is not particularly limited. Flow resistance per unit thickness of the foam as another sound-absorbing material, preferably 100000000N · s / ^{m 4} or less, more preferably 80000000N · s / ^{m 4} or less, more preferably 50000000N · s / ^{m 4} or less.

The shear modulus can be measured by the following method.
First, two test pieces of another flat sheet-shaped sound absorbing material having a thickness of d1 and an area of the main surface of s1 are prepared.
As a device for measuring the shear modulus, a device including a plate for applying a shearing force to the test piece and a vibrator for moving the plate is used. The area of the main surface of the plate is substantially equal to the area s1 of the test piece described above. The aforementioned plate is connected to the exciter. An impedance head for measuring the force F applied to the test piece and the vibration velocity ν is provided between the plate and the exciter. The measuring device includes two base plates for sandwiching and fixing the two test pieces.
Set the test pieces so that the plates are sandwiched between the main surfaces of the two test pieces, and then make sure that the main faces of the two base plates are in contact with the surfaces of the two test pieces that are not in contact with the plates. The two test pieces sandwiching the plate are further sandwiched between the base plates and fixed.
Next, a force is applied to the plate by the exciter, and the force F applied to the test piece and the vibration velocity ν of the test piece are measured by the impedance head. Based on the measured F and ν, the resonance frequency fr1 of mobility M (ω) = ν / F is calculated.
Using the above-mentioned d1, s1, fr1, and m1 which is the sum of the mass of the plate and the mass of the impedance head on the test piece side of the force sensor provided by the impedance head, the shear modulus N is according to the following equation. Is calculated.
Shear modulus N = (m1 × d1) / (2 × s1) × (2π × fr1) ²

The flow resistance per unit thickness can be measured according to ISO 9053.

The shear modulus can be adjusted by adjusting the volume density of the other sound absorbing material. The higher the volume density of the other sound absorbing material, the higher the shear modulus of the other sound absorbing material tends to be.
The flow resistance per unit thickness can be adjusted by adjusting the Young's modulus of other sound absorbing materials. When the porosity of the other sound absorbing material is about the same, the larger the Young's modulus of the other sound absorbing material, the larger the flow resistance per unit thickness tends to be.

The porosity φ of the other sound absorbing material is calculated from the density ρm of the material constituting the other sound absorbing material, the air density ρA, and the bulk density ρtot of the sound absorbing material based on the following formula.
Porosity φ = (ρm-ρtot) / (ρm-ρA)

Young's modulus can be measured by the following method.
First, a test piece of another sound absorbing material in the form of a flat sheet having a thickness of d2 and an area of the main surface of s2 is prepared.
As the Young's modulus measuring device, a device including a base plate on which the test piece is placed, a vibrator for moving the base plate, and a plate for sandwiching and fixing the test piece together with the base plate is used. The base plate is connected to the exciter so that it can move perpendicular to the plane direction of the main surface of the base plate. A pickup for detecting the acceleration α0 is connected to a position on the base plate where the test piece is not placed. Further, a pickup for detecting the acceleration α1 is connected to the surface of the plate opposite to the surface in contact with the test piece.
Next, the test piece is sandwiched between the base plate and the plate and fixed, and the base plate is moved by the exciter to measure the acceleration α0 and the acceleration α1. From the measurement results of α0 and α1, the transfer function H (ω) = α1 / α0 between α0 and α1 is derived, and the resonance frequency fr2 of the transfer function H (ω) is calculated.
Young's modulus E is calculated according to the following formula using the above-mentioned d2, s2, fr2, and m2 which is the mass of the plate.
Young's modulus E = (m2 × d2) / s2 × (2π × fr2) ²

The shape of the foam as another sound absorbing material is not particularly limited. Examples of the shape of the foam include a sheet shape, a rod shape, a regular polyhedron shape (for example, a cube shape, a regular tetrahedron shape, a regular octahedron shape, etc.), a disk shape, a spherical shape, a hemispherical shape, an indefinite shape, and the like. From the viewpoint that it can be preferably produced by the continuous method, the shape of the foam is preferably sheet-like or rod-like. The rod shape is a shape in a stationary state. Since the foam is flexible, the foam may behave like a string when the rod-shaped foam is moved in a stationary state.

The density of the foam as another sound absorbing material is not particularly limited. The density of the foam is appropriately determined according to the use of the other sound absorbing material and the performance required for the other sound absorbing material. Density of the foam, from the point sound-absorbing characteristics are good, for example, preferably 100 kg / ^{m 3} or less, more preferably 50 kg / ^{m 3,} more preferably from 45 kg / ^{m 3} or less, 40 kg / ^{m 3} or less is more preferable. When the density is within this range, it is lightweight and easy to carry on a daily basis, and it is easy to install other sound absorbing materials on buildings and the like, and to attach other sound absorbing materials to various articles. The lower limit of the density of the foam is not particularly limited. The density of the foam is, for example, preferably 10 kg / m ³ or more, and more preferably 20 kg / m ³ or more.

The hardness of the foam is not particularly limited. The hardness of the foam is appropriately determined according to the use of the foam and the performance required for the foam. The hardness of the foam is preferably 50 or less, more preferably 15 or less, still more preferably 10 or less, as the ASKER FP hardness measured at 23 ° C.

Regarding the foam as another sound absorbing material, the total of the content of the inorganic fine particles of the foam and the content of the metal atom contained in the foam as a metal salt of the foam is 2.5% by weight or less. Is preferable, 2% by weight or less is more preferable, 1.5% by weight or less is further preferable, and 1% by weight or less is even more preferable. When the contents of the inorganic fine particles and the metal salt satisfy the above-mentioned requirements, for example, sound absorption in a low frequency band of 1000 Hz or less is less likely to be inhibited.

For other sound absorbing materials, the vertical incident sound absorption coefficient measured using an acoustic tube having an inner diameter of 40 mm and a test piece having a thickness of 10 mm in accordance with JIS A1405-2 at a frequency of 800 Hz is 0.15 or more. It is preferable to show the vertical incident sound absorption coefficient of.
For other sound absorbing materials, at a frequency of 650 Hz, a vertical incident sound absorption coefficient of 0.15 or more measured using an acoustic tube having an inner diameter of 40 mm and a test piece having a thickness of 10 mm in accordance with JIS A1405-2 is vertical. It is more preferable to indicate the incident sound absorption coefficient.
Further, the other sound absorbing material preferably exhibits a vertically incident sound absorption coefficient of 0.4 or more at any frequency in the range of 650 Hz or more and 1200 Hz or less, and any frequency in the frequency range of 650 Hz or more and 1000 Hz or less. It is more preferable to show a vertically incident sound absorption coefficient of 0.4 or more.
Other sound absorbing materials preferably exhibit a vertical incident sound absorption coefficient of 0.5 or more, and more preferably 0.6 or more, at any frequency within the frequency range of 650 Hz or more and 1200 Hz or less. It is preferable to show a vertically incident sound absorption coefficient of 0.7 or more, and more preferably.
In particular, other sound absorbing materials preferably exhibit a vertical incident sound absorption coefficient of 0.5 or more, and exhibit a vertical incident sound absorption coefficient of 0.6 or more at any frequency within the frequency range of 650 Hz or more and 1000 Hz or less. Is more preferable, and it is further preferable to show a vertically incident sound absorption coefficient of 0.7 or more.
Other sound absorbing materials exhibiting such sound absorbing characteristics can easily absorb road noise generated when a vehicle such as an automobile is running. Road noise is noise in a low frequency band generated by elastic vibration of a tire caused by unevenness of a road surface.

Further, for other sound absorbing materials, vertically incident sound absorbing material measured using an acoustic tube having an inner diameter of 40 mm and a test piece having a thickness of 10 mm in accordance with JIS A1405-2 in the frequency range of 1200 Hz or more and 4500 Hz or less. The rate is preferably 0.45 or more, and more preferably 0.5 or more.
In particular, for other sound absorbing materials, vertically incident sound absorbing material measured using an acoustic tube having an inner diameter of 40 mm and a test piece having a thickness of 10 mm in accordance with JIS A1405-2 within a frequency range of 1000 Hz or more and 4500 Hz or less. The rate is preferably 0.45 or more, and more preferably 0.5 or more.
Such other sound absorbing materials can satisfactorily absorb not only low frequency band noise such as road noise but also various noises that may occur in daily life.

As for the foams constituting the other sound absorbing materials, the same as the foams constituting the sound absorbing materials described above, a sample having a thickness of 25 mm was used, and a B tube was used at 20 ° C. in accordance with JIS A 1405-2. It is preferable that the sound absorption coefficient at a frequency of 1000 Hz to 5500 Hz, which is measured in the above manner, is 70% or more.

Further, the foam having a shear modulus of 7,000 Pa or less and a flow resistance per unit thickness of 1,000,000 N · s / m ⁴ or more not only exhibits good sound absorption but also good sound insulation. Also shown.
Here, the sound absorption property is a property that attenuates the sound passing through the material. On the other hand, the sound insulation property is a property of attenuating the reflected sound with respect to the incident sound when the sound incident on the material is reflected.
Specifically, with respect to the foam constituting another sound absorbing material, the vertical incident transmission loss is measured at a frequency of 1000 Hz to 4500 Hz, which is measured by using a sample having a thickness of 10 mm and using an acoustic tube having an inner diameter of 40 mm according to ASTM E2611. It is preferably 7 dB or more.

The foam as another sound absorbing material is preferably composed of a composition containing a polyoxyalkylene polymer because it has good sound absorbing characteristics. Further, since it is easy to manufacture another sound absorbing material and to construct another sound absorbing material, the foam is preferably made of a cured product of a composition containing a base resin having a reactive silicon group.
From the above, the foam is preferably composed of a cured product of a curable composition containing a polyoxyalkylene polymer having a reactive silicon group. Further, since it is particularly easy to achieve both the desired shear modulus and the flow resistance per unit thickness, the foam contains a polyoxyalkylene polymer having a reactive silicon group and a reactive silicon group. It is more preferably composed of a cured product of a curable composition containing the (meth) acrylic resin.

Hereinafter, a resin composition that can be suitably used for producing a foam as another sound absorbing material will be described.

<Resin composition>
Suitable resin compositions for forming foams include a base resin (A) having a reactive silicon group, a chemical foaming agent (B), and a silanol condensation catalyst (D).
The resin composition for a foam preferably contains a dicarbonate diester (B-1) as the chemical foaming agent (B).

[Base resin (A)]
The base resin (A) is as described above.
The base resin (A) is a curable component having a reactive silicon group. The base resin (A) preferably has at least one reactive silicon group in the molecular chain.
Since the base resin (A) has a reactive silicon group, a silanol condensation reaction occurs between the reactive silicon groups to crosslink the resin, and the resin becomes a polymer state and is cured.
The number of reactive silicon groups contained in the base resin (A) is preferably at least one in the molecular chain from the viewpoint of condensation reactivity. From the viewpoint of curability and flexibility, the base resin (A) is preferably a polymer having reactive silicon groups at both ends of the main chain or the molecular chain at the branch portion. The number of such polymers is preferably 1.0 or more and 3.0 or less, more preferably 1.1 or more and 2.5 or less, and particularly preferably 1.2 or more and 2.0 or less in one molecule. It has a reactive silicon group.
The curing reaction of the base resin (A) by the reaction between the reactive silicon groups can be sufficiently proceeded only by the moisture in the air and the material. Therefore, even if the resin composition for foam does not contain water (C) or the content of water (C) is extremely small, there is a particular problem in terms of the progress of curing of the resin composition for foam. There is no.

The structure of the base resin (A) may be linear or has a branched structure, but the branched structure is preferable from the viewpoint of curability.

The molecular weight of the base resin (A) is preferably 1500 or more, more preferably 3000 or more, as the number average molecular weight Mn from the viewpoint of the balance between viscosity and reactivity. The upper limit of the number average molecular weight Mn is not particularly limited, but is preferably 50,000 or less, more preferably 30,000 or less, and even more preferably 30,000 or less. Further, the base resin (A) may be a combination of two or more types. At that time, the polymer other than the polymer used as the main agent may be other than the above conditions if the purpose is to adjust the viscosity and the crosslinked structure.

(In formulas (1) to (3), R ¹ is independently a hydrocarbon group having 1 or more and 20 or less carbon atoms, and the hydrocarbon group as R ¹ may be substituted. It may have a hetero-containing group, where X is a hydroxy or hydrolyzable group, a is 1, 2, or 3, R ⁴ is a divalent linking group, and R ⁴ has two. The bonders are bonded to carbon atoms, oxygen atoms, nitrogen atoms, or sulfur atoms in the linking group, respectively, and R ² and R ³ are independently hydrogen atoms and carbon atoms of 1 to 20 or less, respectively. It is either an alkyl group, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a silyl group.)
The group represented by and the following formula (4):
-R ^5- CH _2- Si (R ¹ ) _3-a (X) _a (4)
(In the formula (4), ^{R 1,} and a is the same as ^{R 1,} and a in equation (1) to (3), ^{R 5} is a hetero atom which may be substituted.)
The group represented by is also preferable.

The X in the formulas (1) to (4) is as described above for the formula (1a).

The main chain structure of the base resin (A) will be described below.

[Main chain structure]
As described above, the main chain structure of the base resin (A) may be linear or may have a branched chain.
The main chain structure of the base resin (A) is not particularly limited, and as the base resin (A), a polymer containing a main chain skeleton having various main chain structures can be used.
Examples of the polymer constituting the main chain skeleton of the base resin (A) include a polyoxyalkylene polymer, a hydrocarbon polymer, a polyester polymer, a vinyl (co) polymer, and (meth) acrylic. Acid ester-based (co) polymer, graft polymer, polysulfide-based polymer, polyamide-based polymer, polycarbonate-based polymer, polymer having urethane bond and / or urea bond (urethane prepolymer), diallyl phthalate-based polymer Etc. can be given.

Examples of the (meth) acrylic acid ester-based (co) polymer include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and (meth) acrylate. ) Examples thereof include (co) polymers obtained by radical polymerization of (meth) acrylic acid ester monomers such as stearyl acrylate, alone or in combination of two or more. The (meth) acrylic acid ester-based (co) polymer is a so-called acrylic resin.

The glass transition temperature of the polymer constituting the main chain skeleton of the base resin (A) is not particularly limited, but is preferably 20 ° C. or lower, more preferably 0 ° C. or lower, and −20 ° C. or lower. Is particularly preferable. If the glass transition temperature exceeds 20 ° C., the viscosity of the resin composition for foam in winter or cold regions may increase, which may result in poor workability, and the flexibility of the foam may decrease, resulting in elongation. May decrease. The glass transition temperature shows the value measured by DSC.

It is also preferable that the base resin (A) contains a resin having a glass transition temperature of 35 ° C. or higher. In this case, it is easy to suppress the shrinkage of the foam after foaming. From the viewpoint that shrinkage of the foam after foaming is particularly easy to be suppressed, the base resin (A) contains a resin having a glass transition temperature of 35 ° C. or higher and a resin having a glass transition temperature of less than 35 ° C. preferable.
The glass transition temperature of the base resin (A) can be adjusted by adjusting the type of the main chain skeleton, the type of the unit constituting the main chain, the composition of the unit constituting the main chain, the molecular weight, and the like.

Among the polymers constituting the main chain skeleton of the base resin (A), the polyoxyalkylene polymer and the acrylic resin are preferable because they have high moisture permeability and the like. A polyoxyalkylene polymer is more preferable, and a polyoxypropylene polymer is most preferable, because the sound absorbing property of the foam is particularly excellent.
Further, from the viewpoint that it is easy to suppress shrinkage of the foam after foaming, and it is easy to obtain a foam showing a desired shear modulus and a flow resistance per unit thickness, the base resin (A) is used. Preferably contains a (meth) acrylic resin together with a polyoxyalkylene polymer.
When the base resin (A) contains a (meth) acrylic resin and a polyoxyalkylene polymer, it is particularly easy to obtain a foam exhibiting a desired shear elasticity and a flow resistance per unit thickness. Therefore, the amount of the (meth) acrylic resin in 100 parts by weight of the base resin (A) is preferably 2 parts by weight or more and 50 parts by weight or less, more preferably 5 parts by weight or more and 40 parts by weight or less, and 8 parts by weight or more and 30 parts by weight. Less than a part is more preferable.
In this case, the amount of the polyoxyalkylene polymer in 100 parts by weight of the base resin (A) is preferably 50 parts by weight or more and 98 parts by weight or less, more preferably 60 parts by weight or more and 95 parts by weight or less, and 70 parts by weight. More than 92 parts by weight or less is more preferable.

Hereinafter, a polyoxyalkylene-based polymer having a reactive silicon group and a (meth) acrylic acid ester-based copolymer, which are particularly preferable among the base resin (A), will be described in detail.

(Polyoxyalkylene polymer)
The main chain structure of the polyoxyalkylene polymer is preferably composed of a repeating unit represented by the following formula (3a).
-R ^4a -O- (3a)
Here, in the formula (3a), R ^4a represents a linear or branched alkylene group having 1 or more and 14 or less carbon atoms, and more preferably 2 or more and 4 or less carbon atoms.

The main chain of the polyoxyalkylene polymer may consist of only one type of repeating unit or may consist of two or more types of repeating units. The polyoxyalkylene polymer is preferably an amorphous polyoxypropylene polymer having a relatively low viscosity.

Examples of the method for synthesizing the polyoxyalkylene polymer include a polymerization method using an alkali catalyst such as KOH; a transition metal such as a complex obtained by reacting an organic aluminum compound shown in JP-A-61-215623 with porphyrin. Compound-Porphyrin Complex Catalyzed Polymerization Method; Japanese Patent Publication No. 46-27250, Japanese Patent Publication No. 59-15336, US Patent No. 3278457, US Patent No. 3278458, US Patent No. 3278459, US Patent No. 3427256, US Patent No. 3427334 , And a polymerization method using a composite metal cyanide complex catalyst (for example, zinc hexacyanocobaltate glyme complex catalyst) shown in US Pat. No. 3,427,335; a weight using a catalyst composed of a polyphosphazene salt shown in JP-A-10-273512. Legal; Examples thereof include a polymerization method using a catalyst composed of a phosphazene compound shown in JP-A-11-060722. The method for synthesizing the polyoxyalkylene polymer is not limited to these.

As the initiator, a compound having at least two active hydrogen groups is preferable. Examples of the active hydrogen-containing compound include polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, and glycerin, and linear or branched polyether compounds having a number average molecular weight of 500 or more and 20000 or less.

Examples of the polyoxyalkylene polymer having a reactive silicon group include JP-A-45-363319, JP-A-46-12154, JP-A-50-156599, and JP-A-54-6096. , Japanese Patent Application Laid-Open No. 55-13767, Japanese Patent Application Laid-Open No. 55-13468, Japanese Patent Application Laid-Open No. 57-164123, Japanese Patent Application Laid-Open No. 362550, US Pat. No. 3632557, US Pat. No. 4345053, US Pat. No. 4,366,307 , US Pat. No. 4,960,844, etc., and the polymers proposed in each publication. Further, Japanese Patent Application Laid-Open No. 61-197631, Japanese Patent Application Laid-Open No. 61-215622, Japanese Patent Application Laid-Open No. 61-215623, Japanese Patent Application Laid-Open No. 61-218632, Japanese Patent Application Laid-Open No. 3-72527, Japanese Patent Application Laid-Open No. 3-72527 The molecular weight distribution is narrow with a number average molecular weight of 6000 or more and a molecular weight distribution (Mw / Mn) of 1.6 or less or 1.3 or less proposed in each of the publications No. 47825 and Japanese Patent Application Laid-Open No. 8-231707. A polyoxyalkylene polymer having a reactive silicon group and the like are also preferable. Such a polyoxyalkylene polymer having a reactive silicon group may be used alone or in combination of two or more.

((Meta) acrylic acid ester-based (co) polymer)
The (meth) acrylic acid ester-based (co) polymer having a reactive silicon group can be obtained by polymerizing various (meth) acrylic acid ester-based monomers alone or in combination of two or more.

The (meth) acrylic acid ester-based (co) polymer can also copolymerize the following vinyl-based monomers together with the (meth) acrylic acid ester-based monomer.

Examples of the (meth) acrylic acid ester-based (co) polymer include a (co) polymer of a (meth) acrylic acid ester-based monomer, a styrene-based monomer and a (meth) acrylic acid-based simple compound from the viewpoint of physical properties and the like. A copolymer with a polymer is preferable, a (co) polymer of a (meth) acrylic acid ester-based monomer is more preferable, and a (co) polymer of an acrylic acid ester-based monomer is further preferable.

The method for producing the (meth) acrylic acid ester-based (co) polymer is not particularly limited. The (meth) acrylic acid ester-based (co) polymer can be produced by a known method. However, a polymer obtained by a normal free radical polymerization method using an azo compound, a peroxide or the like as a polymerization initiator generally has a molecular weight distribution value of more than 2, and tends to have a high viscosity. Therefore, it is a (meth) acrylic acid ester-based (co) polymer having a narrow molecular weight distribution and low viscosity, and has a high proportion of crosslinkable functional groups at the ends of the molecular chain (meth) acrylic acid ester-based (co) weight. In order to obtain coalescence, it is preferable to use the living radical polymerization method.

Among the "living radical polymerization methods", "atom transfer radicals" that polymerize (meth) acrylic acid ester-based monomers using organic halides, sulfonyl halide compounds, etc. as initiators and transition metal complexes as catalysts. In addition to the above-mentioned features of the "living radical polymerization method", the "polymerization method" has halogen and the like at the ends, which are relatively advantageous for the functional group conversion reaction, and has a large degree of freedom in designing the initiator and catalyst. It is more preferable as a method for producing a (meth) acrylic acid ester-based polymer having a specific functional group. This atom transfer radical polymerization method is described, for example, in Mattyjaszewski et al., Journal of the American Chemical Society (J. Am. Chem. Soc), 1995, Vol. 117, p. 5614.

Examples of the method for producing a (meth) acrylic acid ester-based (co) polymer having a reactive silicon group include JP-A-3-14068, JP-A-4-55444, and JP-A-6-21922. Etc., a production method using a free radical polymerization method using a chain transfer agent is disclosed. Further, Japanese Patent Application Laid-Open No. 9-272714 and the like disclose a production method using an atom transfer radical polymerization method. The method for producing a (meth) acrylic acid ester-based (co) polymer having a reactive silicon group is not limited to these methods. The (meth) acrylic acid ester-based (co) polymer having the above-mentioned reactive silicon group may be used alone or in combination of two or more.

The base resin (A) having these reactive silicon groups may be used alone or in combination of two or more. Specifically, when two or more types of base resin (A) are used in combination, the base resin (A) having the same type of main chain may be used in combination, for example, a polymer having a reactive silicon group. A base resin (A) having a different main chain may be used in combination, such as a combination of an oxyalkylene polymer and a (meth) acrylic acid ester polymer having a reactive silicon group.

[Chemical foaming agent (B)]
A suitable foam resin composition contains a chemical foaming agent (B). As the chemical foaming agent (B), a compound that does not generate inorganic fine particles or metal salts as by-products after the foaming reaction is preferable. From this point of view, the chemical foaming agent (B) preferably contains a dicarbonate diester (B-1). After preparing the resin composition for foam, the dicarbonate diester (B-1) is decomposed at a preferable rate according to the rate of the curing reaction of the base resin (A) even under low temperature conditions of about room temperature. Can foam. The dicarbonate diester (B-1) tends to foam better in the presence of water (C) than in anhydrous conditions.
Further, the dicarbonate diester (B-1) produces only a volatile decomposition product after decomposition during foaming. When the foam contains, for example, a large amount of metal salts or the like, it may be difficult to obtain a foam having good sound absorption characteristics in a low frequency band of, for example, 1000 Hz or less. However, when foaming is performed using the dicarbonate diester (B-1), it is possible to easily produce a foam that contains almost no metal salt or the like and exhibits good sound absorption characteristics in a low frequency band.

The resin composition for foams does not contain water (C) or may contain only a small amount of water (C), and achieves a high foaming ratio even when the amount of the chemical foaming agent (B) used is small. From the point of view of ease, it is preferable that the chemical foaming agent (B) is mainly composed of dicarbonate diester (B-1).
The ratio of the weight of the dicarbonate diester (B-1) to the weight of the chemical foaming agent (B) is preferably 50% by weight or more, more preferably 70% by weight or more, further preferably 80% by weight or more, and 90% by weight. The above is particularly preferable, and 100% by weight or more is most preferable.
When the chemical foaming agent (B) contains a chemical foaming agent other than the dicarbonate diester (B-1), the other chemical foaming agents are known as various chemical foaming agents as long as the object of the present invention is not impaired. Agents can be used.
The dicarbonate (B-1) other than the preferred chemical blowing agent (B), tetraisocyanatesilane (Si _{(NCO) 4),} methyl triisocyanate silane _{_{(SiCH 3 (NCO) 3)}} , isocyanatomethyl-trimethoxysilane , Isocyanatomethyltriethoxysilane, 2-isocyanatoethyltrimethoxysilane, 2-isocyanatoethyltriethoxysilane, 3-isocyanato-n-propyltrimethoxysilane, 3-isocyanato-n-propyltriethoxysilane, 4- Examples thereof include isocyanate silane compounds (B-2) such as isocyanato-n-butyltrimethoxysilane and 4-isocyanato-n-butyltriethoxysilane. In particular, isocyanate silane having an alkoxysilyl group is preferable in that it is immobilized on the polymer.
The isocyanate silane compound (B-2) may be used in combination with the dicarbonate diester (B-1).

[Water (C)]
The above-mentioned suitable foam resin composition contains or does not contain water (C). Curing and foaming proceed even when the resin composition for foam does not contain water (C). On the other hand, water (C) has a function of accelerating the foaming reaction of the chemical foaming agent (B) and the curing reaction of the base resin (A).
When the resin composition for a foam contains water (C), the content of water (C) is preferably 1 part by weight or more and 70 parts by weight or less with respect to 100 parts by weight of the base resin (A), and 2 parts by weight. More than 60 parts by weight is more preferable, and 2 parts by weight or more and 50 parts by weight or less is further preferable. When the content of water (C) is within the above range, it is easy to proceed with curing satisfactorily while sufficiently foaming, and it is easy to obtain a foam having fine and dense foam cells and excellent flexibility.

The content of water (C) is preferably 0.05 parts by weight or more, and more preferably 0.1 parts by weight or more with respect to 1 part by weight of the dicarbonate diester (B-1). By using such an amount of water, the dicarbonate diester (B-1) can be satisfactorily reacted with water (C) to cause particularly good foaming, and the base resin (A) can be formed. The hydrolysis-condensation reaction between the reactive silicon groups has proceeded well.
In particular, when the foam resin composition contains only dicarbonate diester (B-1) as the chemical foaming agent (B), the content of water (C) in the foam resin composition is the dicarbonate diester (B-1). B-1) It is preferably 0.05 parts by weight or more and 0.5 parts by weight or less, and more preferably 0.05 parts by weight or more and 0.3 parts by weight or less with respect to 1 part by weight.
In this case, the content of water (C) in the foam after forming the foam can be reduced while causing particularly good foaming, and drying is performed to remove volatile components such as water during the production of the foam. The step can be omitted.
From the viewpoint of reducing the content of water (C) in the foam, the content of water (C) in the resin composition for foam is based on 1 part by weight of the dicarbonate diester (B-1). , 0 parts by weight or more and 0.05 parts by weight or less, more preferably 0 parts by weight or more and 0.03 parts by weight or less, and particularly preferably 0 parts by weight, that is, no water (C) is contained.
In addition, 1 mol of dicarbonate diester (B-1) reacts with 1 mol of water (C) to generate 2 mol of carbon dioxide gas (carbon dioxide). Therefore, from the viewpoint of efficiently foaming the dicarbonate diester (B-1) with water (C) in the resin composition for foam, the dicarbonate diester (B-1) and water (C) are used. The molar ratio of dicarbonate diester (B-1): water (C) is preferably 0.8: 1 to 1: 0.8, preferably 0.9: 1 to 1: 0.9. More preferably, it is 0.95: 1 to 1: 0.95.
The reason why foaming occurs well from the dicarbonate diester (B-1) even when water (C) is insufficient is unknown, but the water content of the dicarbonate diester (B-1) is added to the water in the air and in the material. It is considered that carbon dioxide is generated by decomposition or a decomposition reaction different from hydrolysis.

[Silanol condensation catalyst (D)]
The resin composition for a foam contains a silanol condensation catalyst (D). The silanol condensation catalyst (D) is not particularly limited as long as it can be used as a condensation catalyst, and any one can be used, but the carbonic acid generated by the foaming reaction of the dicarbonate diester (B-1) can be used. A neutral or weakly acidic silanol condensation catalyst (D) is preferable because the catalytic activity is unlikely to decrease due to the influence. Carbonic acid is generated when carbon dioxide dissolves in water.

The catalytic activity is unlikely to decrease due to the influence of carbon dioxide generated by the foaming reaction of the dicarbonate diester (B-1), and the foaming reaction between the dicarbonate diester (B-1) and water and the curing of the base resin (A) Among the silanol condensation catalysts (D) listed above, a neutral or weakly acidic silanol condensation catalyst is preferable, and a weakly acidic silanol condensation catalyst is more preferable, from the viewpoint of allowing the reaction to proceed in a particularly well-balanced manner. Carbonic acid is generated when carbon dioxide dissolves in water.
Further, when a neutral or weakly acidic silanol condensation catalyst is used, it is difficult to inhibit the progress of the foaming reaction of the dicarbonate diester (B-1) with water at the start of foaming.
The silanol condensation catalyst (D) is a neutral or weakly acidic catalyst among the various tin-containing catalysts described above as a neutral or weakly acidic silanol condensation catalyst because the base resin (A) can be easily cured. Is preferably included.
From this point of view, dialkyltin dicarboxylates are preferable as the neutral or weakly acidic tin-containing catalyst with respect to the silanol condensation catalyst (D).
As the neutral or weakly acidic dialkyltin dicarboxylate, a compound represented by the following formula (D1) or an oligomer or polymer composed of a structural unit represented by the following formula (D2) is preferable.
(R ^d1 ) (R ^d2 ) (R ^d3 COO) (R ^d4 COO) Sn ... (D1)
-(-(R ^d1 ) (R ^d2 ) Sn-OCOR ^d5 COO-)-... (D2)
In formulas (D1) and (D2), R ^d1 and R ^d2 may be the same or different, respectively. R ^d1 and R ^d2 are linear or branched alkyl groups, and a linear alkyl group is preferable. The number of carbon atoms of the alkyl group as R ^d1 and R ^d2 is not particularly limited, and is preferably 1 or more and 20 or less, more preferably 2 or more and 16 or less, and further preferably 3 or more and 10 or less. Since the tin-containing catalyst is easily available and the activity of the tin-containing catalyst as a silanol condensation catalyst (D) is good, n-butyl group and n-octyl group are used as R ^d1 and R ^d2. preferable.
In the formula (D1), R ^d3 and R ^d4 are organic groups having 1 or more and 40 or less carbon atoms, respectively. The number of carbon atoms of the organic group as R ^d3 and R ^d4 is preferably 1 or more and 30 or less. The organic groups as R ^d3 and R ^d4 may contain heteroatoms such as O, S, N, and Si.
Since the tin-containing catalyst is easily available and the activity of the tin-containing catalyst as a silanol condensation catalyst (D) is good, the R ^d3 and R ^d4 are linear with 1 to 30 carbon atoms. Alternatively, a branched alkyl group and the following formula (D3):
-CH = CH-CO-OR ^d6 ... (D3)
The group represented by is preferable. R ^d6 is a hydrocarbon group having 1 or more and 30 or less carbon atoms. The hydrocarbon group may be an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a combination of an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The number of carbon atoms of the hydrocarbon group as R ^d6 is preferably 1 or more and 20 or less.
In the formula (D2), R ^d5 is a divalent organic group having 1 or more and 40 or less carbon atoms. The number of carbon atoms of the organic group as R ^d5 is preferably 1 or more and 30 or less, more preferably 1 or more and 10 or less, and further preferably 1 or more and 4 or less. The organic group as R ^d5 may contain heteroatoms such as O, S, N, and Si. As the organic group as R ^d5 , a hydrocarbon group is preferable, and -CH = CH- and -CH ₂ CH ₂ --are more preferable.
Preferable specific examples of the compound represented by the above formula (D1) or the oligomer or polymer composed of the structural unit represented by the above formula (D2) are as described above as specific examples of dialkyltin dicarboxylates. , Dibutyltin diacetate is particularly preferred.
Whether the silanol condensation catalyst is neutral or weakly acidic can be determined by measuring the pH of a water / acetone = 10/90 solution having a concentration of 1% by mass of the silanol condensation catalyst at 20 ° C. Specifically, the case where the pH is 6.0 or more and less than 8.0 is regarded as neutral, and the case where the pH is 3.5 or more and less than 6.0 is regarded as weakly acidic.
When a resin composition for a foam containing a neutral or weakly acidic silanol condensation catalyst (D) is used, foaming and the effect can be easily promoted in a short time. Therefore, the resin composition for a foam containing a neutral or weakly acidic silanol condensation catalyst (D) is particularly useful when constructing a foam at a construction site or a manufacturing site of various industrial products. Is.
This is because foaming and curing in a short time are required for the construction of the foam on site.

The content of the silanol condensation catalyst (D) is preferably 90 parts by weight or less, more preferably 0.05 parts by weight or more and 80 parts by weight or less, and 0.05 parts by weight or more with respect to 100 parts by weight of the base resin (A). 20 parts by weight or less is more preferable, and 1 part by weight or more and 15 parts by weight or less is even more preferable. If the content of the silanol condensation catalyst (D) is more than 80 parts by weight, the foam may bottom out due to compression of the obtained foam. By adjusting the amount of silanol condensation catalyst, the curability of the resin composition for foam can be adjusted.

[Effervescent aid (E)]
The foam resin composition preferably contains a silanol condensation catalyst (D) that acts as a foaming aid (E) and / or a foaming aid (E).
The foaming aid (E) is a component that promotes foaming due to the decomposition of the dicarbonate diester (B-1). The foaming aid (E) is not particularly limited as long as it is a compound that promotes foaming when added to a mixture containing water and a dicarbonate diester (B-1).

[Other additives]
A plasticizer, a reactivity modifier, and a dye can be added to the foam resin composition for the purpose of adjusting the flexibility and molding processability of the foam.

If necessary, a bubble modifier may be added to the foam resin composition. The type of the bubble adjusting agent is not particularly limited, and examples thereof include inorganic solid powders such as talc, magnesium oxide, titanium oxide, zinc oxide, carbon black, and silica, which are usually used. These may be used alone or in combination of two or more.
However, the inorganic solid powder tends to inhibit the sound absorption of the foam in the low frequency band. Therefore, when an inorganic solid powder is used, the amount used is preferably a small amount so that sound absorption in the low frequency band is not excessively hindered.

The amount of the hollow particles used is preferably 0.2 parts by weight or more and 30 parts by weight or less, and more preferably 0.5 parts by weight or more and 15 parts by weight or less with respect to 100 parts by weight of the base resin (A).

Further, a lubricant can be added for the purpose of improving the compatibility of the foam resin composition containing the base resin (A), the chemical foaming agent (B), and water (C).

The multi-component resin composition preferably contains a first liquid containing the base resin (A), a dicarbonate ester (B-1), and at least a second liquid containing a silanol condensation catalyst (D). ..
It is also preferable that the second liquid contains water (C). When the silanol condensation catalyst (D) is contained in the first liquid, curing due to cross-linking between the base resin (A) may proceed. However, by containing the silanol condensation catalyst (D) in a liquid different from the first liquid, it is possible to prevent the base resin (A) from being cured before the foam is produced. When the second liquid contains a silanol condensation catalyst (D), the silanol condensation catalyst (D) preferably contains a neutral or weakly acidic silanol condensation catalyst, and more preferably contains a weakly acidic silanol condensation catalyst.

Further, in the multi-component resin composition, the foaming aid (E) and / or the foaming aid (E) are added to the second liquid containing the silanol condensation catalyst (D) or the liquids other than the first liquid and the second liquid. ), It is preferable to contain a silanol condensation catalyst (D).

[Manufacturing method of foam]
The method for producing a foam using the preferable resin composition for a foam described above may be, for example, a batch method in which the resin composition for a foam is filled in a mold, and then foamed and cured in the mold. Often, a continuous type may be used in which the foam resin composition is continuously foamed and cured on a continuously moving band-shaped support. A non-woven fabric can be used as the support.

Further, the above resin composition for a foam is completely liquid or insoluble in a pigment (for example, carbon black) by using dicarbonate diester (B-1) as the chemical foaming agent (B). Can be made into a low viscosity composition containing only a small amount of.
When the resin composition for foam has a low viscosity, a one-component, two-component or more multi-component resin composition for foam is discharged onto the construction surface and collided and mixed on the construction surface. It is possible to form a film-like foam on the construction surface.

The foam is typically a mixture of a base resin (A) having a reactive silicon group, a first liquid containing a dicarbonate diester (B-1), and a silanol condensation catalyst (D). Manufactured by a method involving a mixing step to obtain a liquid.
In this method, in the mixed solution, the foaming rate due to the decomposition of the dicarbonate diester (B-1) and the rate of the curing reaction of the mixed solution due to the reaction between the reactive silicon groups are 2 times or more and 60 times or less. Each is adjusted so that a foam is obtained.

The foaming rate due to the decomposition of the dicarbonate diester (B-1) is determined by, for example, the type and amount of the dicarbonate diester (B-1) used, the content of water (C) in the mixed solution, and the environment for producing the foam. It can be adjusted by appropriately changing the temperature and the type and content of the silanol condensation catalyst (D) acting as the foaming aid (E) and / or the foaming aid (E) in the mixed solution.
The rate of curing reaction of the mixed solution is, for example, the type and amount of reactive silicon contained in the base resin (A), the type and content of the silanol condensation catalyst (D) in the mixed solution, and the water in the mixed solution ( It can be adjusted by appropriately changing the content of C), the temperature of the environment in which the foam is produced, and the like.
The foaming rate due to the decomposition of the dicarbonate diester (B-1) and the curing reaction rate of the mixed solution are preferably adjusted so that the foaming ratio of the obtained foam is 2 times or more and 60 times or less. It is more preferable that the foaming ratio is adjusted to be 5 times or more and 40 times or less.

The amount of the dicarbonate diester (B-1) used and the amount of the silanol condensation catalyst (D) used in the above production method are as described above for the composition.
The amount of the dicarbonate diester (B-1) used is preferably 1 part by weight or more and 50 parts by weight or less with respect to 100 parts by weight of the base resin (A), and more preferably 2 parts by weight or more and 40 parts by weight or less. 5, 5 parts by weight or more and 30 parts by weight or less are particularly preferable.
The amount of the silanol condensation catalyst (D) used is preferably 0.05 parts by weight or more and 20 parts by weight or less with respect to 100 parts by weight of the base resin (A), and more preferably 1 part by weight or more and 15 parts by weight or less. ..

The foam produced in this manner is preferably distributed and sold as another sound absorbing material after being dried.
The conditions of the drying temperature and time are not particularly limited as long as they can be derived from the resin composition for foam or the water, alcohol, etc. produced by the curing reaction can be reduced to a desired degree. The drying conditions may be, for example, about 1 hour in an atmosphere of about 80 ° C. The drying temperature and time conditions may be, for example, about 12 hours in an atmosphere of about 60 ° C.
However, as described above, when only dicarbonate diester is used as the chemical foaming agent (B) and the amount of water (C) used is set low, it is possible to use other sound absorbing material products without drying. Is.

Further, the resin composition used for forming the foams constituting the other sound absorbing materials described above is usually liquid and exhibits good fluidity. Therefore, the resin composition can be satisfactorily filled and foamed even in a mold having fine flow paths and recesses. Further, since the foaming pressure is small, a simple mold can be used.
Therefore, for the production of the mold used for the production of the foam using the resin composition, a 3D printer capable of easily producing the mold having an internal shape which is fine or complicated is preferably used. be able to.
Therefore, forming a formwork using a 3D printer
Injecting a liquid resin composition containing a polyoxyalkylene polymer (A1) having a reactive silicon group into a mold, and
The foam or the other sound absorbing material described above can be satisfactorily produced by a method including the formation of a foam by curing the resin composition while foaming.
The material of the mold formed by using the 3D printer is not particularly limited, but it is preferably a transparent and lightweight resin material whose contents can be confirmed.
When the resin composition is a multi-component resin composition, a plurality of liquids constituting the multi-component resin composition may be injected into the mold simultaneously or sequentially, and the plurality of liquids are mixed. It may be injected into the mold in a state, and it is preferable to inject into the mold in a state where a plurality of liquids are mixed.

≪Sound absorption method≫
Various sounds, especially noise, can be absorbed by using the other sound absorbing materials described above. Since the above-mentioned other sound absorbing material can absorb sound in a wide frequency band, it is preferable to use the above-mentioned other sound absorbing material to absorb sound containing a component having a frequency in the range of 650 Hz or more and 4500 Hz or less.
Further, since the other sound absorbing material described above can absorb sound in a low frequency band, it is preferable to use the other sound absorbing material described above to absorb sound containing a component having a frequency in the range of 650 Hz or more and 1000 Hz or less. ..

≪Sound insulation method≫
Various sounds, especially noise, can be insulated by using the other sound absorbing materials described above. Since the above-mentioned other sound absorbing materials can absorb sound in a wide frequency band and at the same time can insulate sound in a wide frequency band, the other sound absorbing materials mentioned above can be used in a frequency range of 1000 Hz or more and 4500 Hz or less. It is preferable to insulate the sound containing the above components while absorbing it by another sound absorbing material.
As a result, the sound passing through the other sound absorbing material is significantly attenuated, and the sound reflected by the other sound absorbing material is also significantly attenuated.
For example, in a support composed of a motor and a casing accommodating the motor, in a sound absorbing structure described later in which a gap between the motor and the casing is filled with another sound absorbing material, the motor is inside the sound absorbing structure. Since the generated noise can be absorbed while being insulated, the operation of the motor can be made extremely quiet.
In the above sound absorbing structure, it is difficult to achieve both sound absorbing property and sound insulating property with conventionally known foams. This is because both mechanisms are in conflict. Since the conventional sound absorbing material absorbs and attenuates sound by passing sound waves, it is difficult to improve the sound insulation. Further, since the sound insulating material reflects sound waves without passing through them, sound leaks from the gaps in a casing having a gap, and soundproofing cannot be improved.

≪Sound absorbing structure≫
The sound absorbing structure includes the above-mentioned other sound absorbing material and a support that supports the other sound absorbing material. The support is not particularly limited as long as it can support other sound absorbing materials. The support is not particularly limited, and may be a cloth, a plate made of resin, wood, or gypsum, or a pipe made of resin or wood.

For example, examples of sound absorbing structures for buildings include sound absorbing structures in which other sheet-shaped sound absorbing materials are supported on resin, wooden, or gypsum boards, or inside resin, wooden, or gypsum. Examples thereof include a sound absorbing structure composed of a box-shaped sheet-shaped member having a cavity and another sound absorbing material filled in the cavity inside the sheet-shaped member.
Such other sound absorbing materials can be used as materials for walls, floors, and ceilings in buildings.

Further, in vehicle applications, the sound absorbing structure may be formed by supporting the other sound absorbing materials described above on exterior materials and interior materials such as doors, bonnets, roofing materials (roofs), floor materials, fenders, pillars, and seats.
As the sound absorbing structure for a vehicle, a sound absorbing structure in which another sound absorbing material is supported by the pneumatic tire so as to cover at least a part of the surface on the lumen side of the pneumatic tire is also preferable.
According to the sound absorbing structure provided with the pneumatic tire as a support, it is easy to suppress the propagation of road noise into the vehicle.
Further, a sound absorbing structure in which the support is composed of a motor and a casing accommodating the motor, and the gap between the motor and the casing is filled with another sound absorbing material is also preferable.
Examples of the motor include a drive motor, a pump motor, a power generation motor, a fan motor, a power generation motor, an electric power steering motor, a blower motor for an air conditioner and an air cooling device, which are mounted on electric vehicles and hybrid vehicles. Examples include motors for power windows and motors for electric power seats.
According to such a sound absorbing structure including a motor, it is possible to suppress the propagation of noise caused by driving the motor from the sound absorbing structure to the outside of the sound absorbing structure, and to reduce the noise in the space inside the vehicle.

≪Manufacturing method of sound absorbing structure≫
The above-mentioned sound absorbing structure can be manufactured by fixing another sound absorbing material to the surface of the support or filling the space defined by the support with the other sound absorbing material.
As a method of fixing the other sound absorbing material to the surface of the support, a method using a fixture such as a nail, a screw, a screw, or a clip may be used, or a method using an adhesive, an adhesive tape or the like may be used. ..

When the resin composition for a foam used for forming a foam as another sound absorbing material is a liquid curable composition containing a polyoxyalkylene polymer (A1) having a reactive silicon group, it is liquid. The curable composition is applied to the surface of the support and then cured while foaming the liquid curable composition, or the space defined by the support is filled with the liquid curable composition and then the liquid curable. A sound absorbing structure can be produced by curing the composition while foaming it.
The foaming and curing of the liquid curable composition is carried out according to the above-mentioned method for producing a foam.
When the liquid curable composition is filled in the space defined by the support and then cured while foaming the liquid curable composition, the support is provided with a vent for releasing the gas generated by the foaming reaction. It is preferable that it is.
Since the cured product of the liquid curable composition containing the oxyalkylene polymer (A1) having a reactive silicon group has adhesiveness to various materials, a sound absorbing structure can be produced by the above method. ..

More specifically, a liquid curable composition containing an oxyalkylene polymer (A1) having a reactive silicon group is applied to the inner surface of the tire as a support, and then the applied liquid. By curing the curable composition while foaming it, a tire provided with another sound absorbing material can be produced as a sound absorbing structure.

Further, in the support composed of the motor and the casing accommodating the motor, after filling the gap between the motor and the casing with a liquid curable composition containing the oxyalkylene polymer (A) having a reactive silicon group. By curing the filled liquid curable composition while foaming, a sound absorbing structure containing a motor in a casing can be manufactured.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
Unless otherwise specified, "parts" and "%" in Examples and Comparative Examples indicate "parts by weight" and "% by weight".

[Synthesis Example 1]
<Polymer A>
Polyoxypropylene triol having a molecular weight of about 3,000 was used as an initiator, and propylene oxide was polymerized with a zinc hexacyanocovalent glyme complex catalyst, and the number average molecular weight was 16,400 (using HLC-8120GPC manufactured by Tosoh as a liquid feeding system). , TSK-GEL H type manufactured by Tosoh Co., Ltd. was used as the column, and polystyrene-equivalent molecular weight measured using THF was used as the solvent to obtain hydroxy group-terminated polyoxypropylene. Subsequently, 1.2 times equivalent of a methanol solution of NaOMe was added to the hydroxy group of the hydroxy group-terminated polyoxypropylene to distill off methanol, and 1.5 times equivalent of 3-chloro-1-propene was added. It was added to convert the terminal hydroxy group to an allyl group. Next, to 100 parts by weight of the obtained allyl group-terminated polyoxypropylene polymer, 36 ppm of a platinum divinyldisiloxane complex (isopropyl alcohol solution of 3% by weight in terms of platinum) was added, and while stirring, 3.3 weight by weight of triethoxysilane. The portion was slowly added dropwise and reacted at 90 ° C. for 2 hours. Further, 30 parts by weight of methanol and 12 ppm of HCl are added to convert the ethoxy group at the terminal into a methoxy group, and then excess methanol is removed to form a branched product having 2.1 trimethoxysilyl groups at the terminal in one molecule. Reactive silicon group-containing polyoxypropylene was obtained. The glass transition temperature of the polymer is −60 ° C.

[Synthesis Example 2]
<Polymer B>
Polyoxypropylene glycol having a number average molecular weight of about 2,000 was used as an initiator, and propylene oxide was polymerized using a zinc hexacyanocobaltate glyme complex catalyst to obtain a number average molecular weight of 27900 (Tosoh HLC-8120GPC as a liquid feed system). The column used was TSK-GEL H type manufactured by Tosoh, and the solvent was polystyrene-equivalent molecular weight measured using THF) to obtain hydroxy group-terminated polyoxypropylene. Subsequently, 1.05 times equivalent of a methanol solution of NaOMe was added to the hydroxyl group of the hydroxy group-terminated polyoxypropylene to distill off methanol, and 1.16 times equivalent of propargyl bromide was added to the terminal. The hydroxyl group was converted to a propargyl group. The obtained unpurified propargyl group-terminated polyoxypropylene was mixed with n-hexane and water, and then water was removed by centrifugation. Hexane was devolatile from the obtained hexane solution under reduced pressure to give the polymer. The metal salt was removed. From the above, polyoxypropylene having a propargyl group at the terminal site was obtained. To 500 g of this polymer, 150 μL of a platinum divinyldisiloxane complex (3 wt% isopropyl alcohol solution in terms of platinum) and 8.37 g of trimethoxysilane were added, reacted at 90 ° C. for 2 hours, and then unreacted. By distilling off trimethoxysilane under reduced pressure, polyoxypropylene having a trimethoxysilyl group at the terminal and having a number average molecular weight of 28500 was obtained. Such polyoxypropylene has a terminal structure in which trimethoxysilane is added to a propargyl group. It was found that the obtained polyoxypropylene had an average of 2.0 trimethoxysilyl groups in one molecule. The glass transition temperature of the polymer is −60 ° C.

[Preparation Example 1]
<Polymer D>
60 parts by weight of polymer A, methyl methacrylate (MMA), 2-ethylhexyl acrylate (2EHA), stearyl methacrylate (SMA), 3- (trimethoxysilyl) propyl methacrylate (TSMA), and (3-mercaptopropyl). 40 parts by weight of the copolymer of trimethoxysilane (A189Z) and 27 parts by weight of isobutyl alcohol which is the solvent of the copolymer are degassed and uniformly mixed using a rotary evaporator, and a reactive silicon group-containing polyoxy is mixed. A polymer D having a solid content of 100%, which is a blend of 60 parts by weight of propylene (polymer A) and 40 parts by weight of acrylic resin, was obtained.
The copolymerization ratio (mass ratio) of the copolymer is 65/24/1/10/8 as MMA / 2EHA / SMA / TSMA / A189Z. The glass transition temperature of the copolymer is 43 ° C. The number average molecular weight of the polymer is 2,200 (polystyrene-equivalent molecular weight measured using HLC-8120GPC manufactured by Tosoh as a liquid feeding system, TSK-GEL H type manufactured by Tosoh as a column, and THF as a solvent). is there.

[Preparation Example 2]
<Polymer E>
60 parts by weight of polymer A, methyl methacrylate (MMA), butyl acrylate (BA), 2-ethylhexyl acrylate (2EHA), stearyl methacrylate (SMA), 3- (trimethoxysilyl) propyl methacrylate (TSMA), Using a rotary evaporator, 40 parts by weight of a copolymer of tert-butyl methacrylate (tBMA) and (3-mercaptopropyl) trimethoxysilane (A189Z) and 27 parts by weight of isobutyl alcohol which is a solvent of the copolymer are used. After degassing and uniformly mixing, 60 parts by weight of the reactive silicon group-containing polyoxypropylene (polymer A) and 40 parts by weight of the acrylic resin were blended to obtain a polymer E having a solid content of 100%.
The copolymerization ratio (mass ratio) of the copolymer is 64 / 0.3 / 0.3 / 10/10/15 / 7.2 as MMA / BA / 2EHA / SMA / TSMA / tBMA / A189Z. .. The glass transition temperature of the copolymer is 70 ° C. The number average molecular weight of the polymer is 2,300 (polystyrene-equivalent molecular weight measured using HLC-8120GPC manufactured by Tosoh as a liquid feeding system, TSK-GEL H type manufactured by Tosoh as a column, and THF as a solvent). is there.

[Preparation Example 3]
<Polymer F>
60 parts by weight of polymer A, methyl methacrylate (MMA), butyl acrylate (BA), 2-ethylhexyl acrylate (2EHA), stearyl methacrylate (SMA), 3- (trimethoxysilyl) propyl methacrylate (TSMA), Using a rotary evaporator, 40 parts by weight of a copolymer of isoboronyl methacrylate (iBOMA) and (3-mercaptopropyl) trimethoxysilane (A189Z) and 27 parts by weight of isobutyl alcohol as a solvent for the copolymer were used. Degassed and uniformly mixed to obtain a polymer F having a solid content of 100%, which is a blend of 60 parts by weight of the reactive silicon group-containing polyoxypropylene (polymer A) and 40 parts by weight of the acrylic resin.
The copolymerization ratio (mass ratio) of the copolymer is 20 / 0.3 / 0.3 / 10/10/60 / 1.8 as MMA / BA / 2EHA / SMA / TSMA / iBoMA / A189Z. .. The glass transition temperature of the copolymer is 100 ° C. The elementary average molecular weight of the polymer is 5,300 (polystyrene-equivalent molecular weight measured using HLC-8120GPC manufactured by Tosoh as a liquid feeding system, TSK-GEL H type manufactured by Tosoh as a column, and THF as a solvent). is there.

[Example 1]
Base resin (A) [polymer A] 80 parts by weight, base resin (A) [polymer D] 20 parts by weight, dicarbonate diester (B-1) [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., diethyl dicarbonate ] 10 parts by weight and 4 parts by weight of water (C) were added and mixed thoroughly to prepare a first liquid.
In 114 parts by weight of this first liquid, 2 parts by weight of a foam stabilizer [Ebonic Japan Co., Ltd., Tegostarve BF2470], silanol condensation catalyst (D) [Nitto Kasei Co., Ltd., Neostan U200 (dibutyltin diacetate)] 6 parts by weight and 4 parts by weight of silanol condensation catalyst (D) [DABCO (1,4-diazabicyclo [2.2.2] octane)] are added, and the volume is graduated at room temperature (23 ° C atmosphere). A total of 10 cc was prepared in a resin cup, and the mixture was manually stirred with a 10 mm wide spatula for 10 seconds to foam. Table 1 shows the foaming ratio after 5 minutes from the start of stirring and the density of the foam.
In addition, the ASKER FP hardness of the obtained foam at 0 ° C. was measured. The FP hardness is shown in Table 1.

[Example 2]
Base resin (A) [polymer A] 80 parts by weight, base resin (A) [polymer E] 20 parts by weight, dicarbonate diester (B-1) [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., diethyl dicarbonate ] 10 parts by weight and 2 parts by weight of water (C) were added and mixed thoroughly to prepare a first liquid.
To 112 parts by weight of this first liquid, 2 parts by weight of a foam stabilizer [Ebonic Japan Co., Ltd., Tegostarve BF2470], silanol condensation catalyst (D) [Nitto Kasei Co., Ltd., Neostan U200 (dibutyltin diacetate)] Add 6 parts by weight and 1.2 parts by weight of silanol condensation catalyst (D) [DABCO (1,4-diazabicyclo [2.2.2] octane)], and scale the volume at room temperature (23 ° C atmosphere). A total of 10 cc was prepared in a resin cup with a mark, and the mixture was manually stirred with a 10 mm wide spatula for 10 seconds to foam. Table 1 shows the foaming ratio after 5 minutes from the start of stirring and the density of the foam.
In addition, the ASKER FP hardness of the obtained foam at 0 ° C. was measured. The FP hardness is shown in Table 1.

[Example 3]
40 parts by weight of base resin (A) [polymer A], 60 parts by weight of base resin (A) [polymer F], dicarbonate diester (B-1) [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., diethyl dicarbonate ] 13 parts by weight and 4 parts by weight of water (C) were added and mixed thoroughly to prepare a first liquid.
In addition to 117 parts by weight of the first liquid, 0.3 parts by weight of a foam stabilizer [Ebonic Japan Co., Ltd., Tegostarve BF2470], silanol condensation catalyst (D) [Nitto Kasei Co., Ltd., Neostan U200 (dibutyltin diacetate) )] 4 parts by weight and 1.2 parts by weight of silanol condensation catalyst (D) [DABCO (1,4-diazabicyclo [2.2.2] octane)] were added, and the volume was increased at room temperature (23 ° C. atmosphere). A total of 10 cc was prepared in a resin cup with the scale of No. 1 and hand-stirred with a 10 mm wide spatula for 10 seconds to foam. Table 1 shows the foaming ratio after 5 minutes from the start of stirring and the density of the foam.
In addition, the ASKER FP hardness of the obtained foam at 0 ° C. was measured. The FP hardness is shown in Table 1.

[Comparative Example 1]
Polyurethane foam (urethane sponge sound absorbing material ZS manufactured by Sonorize Co., Ltd.) was used as the foam of Comparative Example 1.

<Measurement of sound absorption coefficient>
The foam of Example 2 for measuring the sound absorption coefficient was prepared according to the following method.
First, 80 parts by weight of [Polymer A], 20 parts by weight of [Polymer E], 10 parts by weight of foaming agent (B-1) [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., diethyl carbonate], and water (C). 2 parts by weight was added and mixed sufficiently to prepare a solution A. 2 parts by weight of the foam stabilizer [Evonik Degussa Japan Co., Ltd., TEGOSTAB BF2470], which is a component of the liquid A and liquid B, and the foaming aid [Evonik Degussa Japan Co., Ltd., DABCO NE1070] 1.2. A foam was prepared by adding 6 parts by weight and 6 parts by weight of Sn catalyst (D) [dibutyltin diacetate (NEOSTANN U-200, manufactured by Nitto Kasei Co., Ltd.)] and thoroughly mixing them. Foam molding was produced by stirring under the following conditions using a stirrer Magella ZZ-2221 manufactured by Tokyo Rika Kikai Co., Ltd.
Stirring speed: 610 rpm
Stirring blade: Circular dispar with a diameter of 4 cm, in which the disc edges are alternately bent vertically with a width of 10 mm and a bending length of 5 mm. Mixing amount: 120 g
Mixing time: Immediately after stirring for 10 seconds, the liquid composition was poured into a 20 cm × 20 cm × 5 cm polyethylene tapper, foamed with the top lid on, and left for 12 hours. The working conditions were 23 ° C. (Foam molding process). The obtained foamed cured product was released from a polyethylene tapper and left to stand in an atmosphere of 23 ° C. for 1 week to obtain a soft resin foam (drying step). The skin layer of the obtained soft resin foam was cut to a thickness of 25 mm or 20 mm, and the B tube sample was punched to a diameter of 29 mm to obtain a sound absorption coefficient measurement sample (skin layer cutting step).
The foam of Example 3 for measuring the sound absorption coefficient was prepared according to the following method.
First, 40 parts by weight of [Polymer A], 60 parts by weight of [Polymer D], 13 parts by weight of foaming agent (B-1) [diethyl carbonate manufactured by Wako Pure Chemical Industries, Ltd.], and 4 parts by weight of water (C). Was added and mixed thoroughly to prepare a solution A. 0.3 parts by weight of the foam stabilizer [Evonik Degussa Japan Co., Ltd., TEGOSTAB BF2470], which is a component of the liquid A and liquid B, and the foaming aid [Evonik Degussa Japan Co., Ltd., DABCO NE1070] 1 .2 parts by weight and 4 parts by weight of Sn catalyst (D) [dibutyltin diacetate (NEOSTANN U-200, manufactured by Nitto Kasei Co., Ltd.)] were added and thoroughly mixed to prepare a foam. Foam molding was produced by stirring under the following conditions using a stirrer Magella ZZ-2221 manufactured by Tokyo Rika Kikai Co., Ltd.
Stirring speed: 610 rpm
Stirring blade: Circular dispar with a diameter of 4 cm, in which the disc edges are alternately bent vertically with a width of 10 mm and a bending length of 5 mm. Mixing amount: 80 g
Mixing time: Immediately after stirring for 10 seconds, the liquid composition was poured into a 20 cm × 20 cm × 5 cm polyethylene tapper, foamed with the top lid on, and left for 12 hours. The working conditions were 23 ° C. (Foam molding process). The obtained foamed cured product was released from a polyethylene tapper and left to stand in an atmosphere of 23 ° C. for 1 week to obtain a soft resin foam (drying step). The skin layer of the obtained soft resin foam was cut to a thickness of 20 mm, and the B tube sample was punched to a diameter of 29 mm to obtain a sound absorption coefficient measurement sample (skin layer cutting step).
As the foam of Comparative Example 1, a urethane sponge sound absorbing material ZS manufactured by Sonorize Co., Ltd. was punched to a diameter of 29 mm to obtain a sound absorption coefficient measurement sample of a B tube.
Using the prepared test piece, the sound absorption coefficient of the foam in the frequency range of 500 Hz to 6400 Hz was measured using a B tube at 20 ° C. according to JISA-1405-2. The test piece is in a state where the skin layer is completely cut.
The measurement result of the sound absorption coefficient is shown in FIG.

<Water gel fraction measurement>
The foam test pieces of Examples 1 to 3 were immersed in water at room temperature (23 ° C. atmosphere) for 3 days and then dried at 100 ° C. for 12 hours. The ratio (%) of the weight of the test piece after drying to the weight of the test piece before immersion in water was defined as the water gel fraction (%). A test piece of about 10 g of foam was immersed in a 225 mL bottle of water.

* 1: Of the silanol condensation catalysts (D), DABCO is DABCO NE1070 and acts as a foaming aid (E).

According to Table 1 and FIG. 1, the sound absorption coefficient measured by a predetermined method by foaming and curing the base resin (A) having a reactive silicon group containing the polyoxyalkylene polymer (A1). It can be seen that a foam having a frequency of 70% or more can be produced in a wide range of frequencies from 1000 Hz to 5500 Hz.
On the other hand, the sound absorption coefficient of the foam of Comparative Example 1, which is a known polyurethane foam, is lower than the sound absorption coefficient of the foam of Example in the entire frequency range in the graph shown in FIG. 1, especially in the range of 800 Hz to 2500 Hz. Low.

Further, according to Examples 1 to 3, it can be seen that when the dicarbonate diester (B-1) is used as the chemical foaming agent (B), the water gel fraction is high and the water resistance of the foam is good. ..

Further, each of the foam of Example 2 and the foam of Example 3 had a thickness of 20 mm, and a test piece having a cut skin layer was prepared. Using the prepared test piece, the sound absorption coefficient of the foam in the frequency range of 500 Hz to 6400 Hz was measured using a B tube at 20 ° C. according to JISA-1405-2. The measurement result of the sound absorption coefficient is shown in FIG.
According to FIG. 2, it can be seen that there is no significant difference in sound absorption coefficient between the foam of Example 2 and the foam of Example 3.

Further, in Examples 1 to 3, metal salts and inorganic fine particles are not used as materials used for producing the foam. In fact, the alkali metal content, especially the sodium content, of the foams obtained in Examples 1 to 3 was confirmed by ICP emission spectroscopy (high frequency inductively coupled plasma emission spectroscopy), but the alkali metal content. Was a very small amount of less than 0.005% by mass.
It is considered that the low content of the metal salt and the inorganic particles in the foam contributes to the high sound absorption of the foam, particularly the high sound absorption at frequencies of 1000 Hz or less and 800 Hz or less.
As a result of the test by the inventor, it was confirmed that the sound absorption property at a frequency of 1000 Hz or less or 800 Hz or less tends to decrease slightly as the content of the metal salt or the inorganic fine particles in the foam increases.

[Examination of the effect on the sound absorption coefficient of the skin layer]
The foam of Example 3 and the foam of Comparative Example 2 (polyurethane foam manufactured by Saint-Gobain, AGP200, density 30 kg / m ³ ) were 20 mm thick, respectively, and the skin layer was cut off. A test piece having the above was prepared. Using the prepared test piece, the sound absorption coefficient of the foam in the frequency range of 500 Hz to 6400 Hz was measured using a B tube at 20 ° C. according to JISA-1405-2.
As a result, with respect to the foam of Example 3, the sound absorption coefficient for each frequency was almost the same between the test piece having the skin layer and the test piece having the skin layer cut.
On the other hand, in the foam of Comparative Example 2, the sound absorption coefficient of the test piece having the skin layer was significantly inferior to the sound absorption coefficient of the test piece having the skin layer cut in the frequency range of 1000 to 3000 Hz.
That is, the foam of Example 3 has a small influence on the sound absorption characteristics with and without the skin layer. For example, when a foam is constructed using a resin composition for a foam at a construction site or a manufacturing site of various products, it may be difficult to cut the skin layer. However, since the foam of the example has a small influence on the sound absorption characteristics of the presence or absence of the skin layer, even if the foam is applied at the construction site or the manufacturing site of various products, the sound absorption characteristics of the foam are sufficiently sufficient. Can be demonstrated.

[Reference example 1]
Base resin (A) [polymer A] 100 parts by weight, dicarbonate diester (B-1) [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., diethyl dicarbonate] 10 parts by weight, and water (C) 2 parts by weight. The first solution was prepared by adding and mixing well.
To 112 parts by weight of this first liquid, 2 parts by weight of a foam stabilizer [Ebonic Japan Co., Ltd., Tegostarve BF2470], silanol condensation catalyst (D) [Nitto Kasei Co., Ltd., Neostan U200 (dibutyltin diacetate)] Made of resin with a volume scale at room temperature (23 ° C atmosphere) with the addition of 6 parts by weight and 4 parts by weight of silanol condensation catalyst [DABCO (1,4-diazabicyclo [2.2.2] octane)]. The mixture was prepared so as to have a total of 10 cc in the cup, and was manually stirred with a 10 mm wide spatula for 10 seconds to foam. Table 2 shows the foaming ratio after 5 minutes from the start of stirring and the density of the foam. Table 2 shows the foaming ratio 24 hours after the start of stirring.

[Comparative Example 2]
Base resin (A) [Polymer C, polyether having dimethoxy (methyl) silylmethyl carbamate terminal, manufactured by WACKER CHEMIE, GENIOSIL (registered trademark) STP E-10] 100 parts by weight, dicarbonate diester (B-1) [Fujifilm Wako Pure Chemical Industries, Ltd., diethyl carbonate] 10 parts by weight and 2 parts by weight of water (C) were added and mixed thoroughly to prepare a first solution. Polymer C is liquid at room temperature. The glass transition temperature of Polymer C is −60 ° C.
To 112 parts by weight of this first liquid, 2 parts by weight of a foam stabilizer [Ebonic Japan Co., Ltd., Tegostarve BF2470], silanol condensation catalyst (D) [Nitto Kasei Co., Ltd., Neostan U200 (dibutyltin diacetate)] 6 parts by weight and 1.2 parts by weight of silanol condensation catalyst [DABCO (1,4-diazabicyclo [2.2.2] octane)] were added, and the volume was graduated at room temperature (23 ° C. atmosphere). The mixture was mixed in a resin cup so as to have a total of 10 cc, and was manually stirred with a 10 mm wide spatula for 10 seconds to foam. Table 2 shows the foaming ratio after 5 minutes from the start of stirring and the density of the foam. Table 2 shows the foaming ratio 24 hours after the start of stirring.

[Example 1]
In the same manner as in Example 1 described above, the first liquid was prepared and the foam was prepared. Table 2 shows the foaming ratio and the density of the foam after 5 minutes from the start of stirring, and the foaming ratio 24 hours after the start of stirring.

[Example 4]
In the first liquid, the amount of water (C) was changed from 4 parts by weight to 2 parts by weight, and the amount of silanol condensation catalyst [DABCO (1,4-diazabicyclo [2.2.2] octane)] was changed to 4 parts by weight. Other than changing from 1 part to 1.2 parts by weight, the first liquid was prepared and the foam was prepared in the same manner as in Example 1. Table 2 shows the foaming ratio and the density of the foam after 5 minutes from the start of stirring, and the foaming ratio 24 hours after the start of stirring.

[Example 5]
In the first liquid, the preparation of the first liquid and the preparation of the foam were carried out in the same manner as in Example 1 except that water (C) was not used. Table 2 shows the foaming ratio and the density of the foam after 5 minutes from the start of stirring, and the foaming ratio 24 hours after the start of stirring.

[Example 2]
In the same manner as in Example 2 described above, the first liquid was prepared and the foam was prepared. Table 2 shows the foaming ratio and the density of the foam after 5 minutes from the start of stirring, and the foaming ratio 24 hours after the start of stirring.

[Example 6]
Except for changing the polymer A to the polymer B, the first liquid was prepared and the foam was prepared in the same manner as in Example 2. Table 2 shows the foaming ratio and the density of the foam after 5 minutes from the start of stirring, and the foaming ratio 24 hours after the start of stirring.

[Example 7]
Except for changing the polymer A to the polymer C, the first liquid and the foam were prepared in the same manner as in Example 2. Table 2 shows the foaming ratio and the density of the foam after 5 minutes from the start of stirring, and the foaming ratio 24 hours after the start of stirring.

* 2: Of the silanol condensation catalysts (D), DABCO is DABCO NE1070 and acts as a foaming aid (E).
* 3: Shrink rate (%) = (foaming ratio after 5 minutes-24 hours after foaming ratio) / 5 minutes after foaming ratio x 100

According to Table 2, in the resin composition for a foam containing the base resin (A) having a reactive silicon group, the chemical foaming agent (B), and the silanol condensation catalyst (D), the base resin (A) ), When the acrylic resin (A2) having a glass transition temperature of 35 ° C. or higher and the polyoxyalkylene polymer (A1) having a glass transition temperature of less than 35 ° C. are used in combination, 24 hours after the start of foaming. It can be seen that the foam hardly shrinks in.
On the other hand, in Reference Example 1 using a foam resin composition containing only the polyoxyalkylene polymer (A1) having a glass transition temperature of less than 35 ° C. as the base resin (A), 24 hours from the start of foaming. Later, a significant shrink of the foam occurred.

The foams obtained in Examples 1, 2 and 4 to 7 are measured using a sample having a thickness of 25 mm and using a B tube at 20 ° C. in accordance with JIS A 1405-2. The sound absorption coefficient at frequencies of 1000 Hz to 5500 Hz was 70% or more.

Hereinafter, the other sound absorbing materials described above will be described with reference to Examples 8, 9, and Comparative Examples 3 to 10. In Examples 8, 9, and Comparative Examples 3 to 5, the polymer A prepared in the above-mentioned Synthesis Example 1 was used as the base resin (A). In Example 8, Comparative Example 4, and Comparative Example 5, the polymer F prepared in Preparation Example 3 described above was used as the base resin (A).

[Example 8]
Polymer A and polymer F as the base resin (A), foaming agent [Fujifilm Wako Pure Chemical Industries, Ltd., diethyl carbonate (B-1)], and foam stabilizer [Evonik Degussa Japan] TEGOSTAB B8244 manufactured by Co., Ltd.] and water (C) were added in the amounts shown in Table 3 and sufficiently mixed to prepare a solution A. In this solution A, the amounts of foaming aid [DABCO NE1070 manufactured by Evonik Degussa Japan Co., Ltd.] and silanol condensation catalyst (D) [tetraethoxysilane-modified dibutyltin salt (Nitto Kasei Co., Ltd.) are added to each of the amounts shown in Table 3. ), NEOSTANN U-700)] was sequentially added and mixed to prepare a foam. Foam molding was produced by stirring under the following conditions using a stirrer Magella ZZ-2221 manufactured by Tokyo Rika Kikai Co., Ltd.
Stirring speed: 610 rpm
Stirring blade: Circular dispar with a diameter of 4 cm, in which the disc edges are alternately bent vertically with a width of 10 mm and a bending length of 5 mm. Mixing amount: 84 g
Mixing time: 10 seconds Immediately after stirring, the mixed liquid composition was poured into a polyethylene tapper of length: 20 cm × width: 20 cm × height: 5 cm, foamed with the upper lid set, and left to stand for 12 hours. The working conditions were 23 ° C. (Foam molding process). The foamed cured product obtained after 12 hours was released from the polyethylene tapper and left to stand in an atmosphere of 80 ° C. for 1 hour to obtain a soft resin foam (drying step). The skin layer of the obtained soft resin foam was cut to a specified thickness, and each measurement sample of the sound absorbing material was prepared (skin layer cutting step).

[Example 9]
Polymer A as the base resin (A), foaming agent [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., diethyl carbonate (B-1)], and foam stabilizer [manufactured by Ebonic Degussa Japan Co., Ltd.] , TEGOSTAB B8244] and water (C) were added in the amounts shown in Table 3 and mixed sufficiently to prepare a solution A. In this solution A, the amounts of foaming aid [DABCO NE1070 manufactured by Evonik Degussa Japan Co., Ltd.] and silanol condensation catalyst (D) [tetraethoxysilane-modified dibutyltin salt (Nitto Kasei Co., Ltd.) are added to each of the amounts shown in Table 3. ), NEOSTANN U-700)] was sequentially added and mixed to prepare a foam. Foam molding was produced by stirring under the following conditions using a stirrer Magella ZZ-2221 manufactured by Tokyo Rika Kikai Co., Ltd.
Stirring speed: 610 rpm
Stirring blade: Circular dispar with a diameter of 4 cm, in which the disc edges are alternately bent vertically with a width of 10 mm and a bending length of 5 mm. Mixing amount: 84 g
Mixing time: 15 seconds Immediately after stirring, the mixed liquid composition was poured into a polyethylene tapper of length: 20 cm × width: 20 cm × height: 5 cm, foamed with the upper lid set, and left to stand for 12 hours. The working conditions were 23 ° C. (Foam molding process). The foamed cured product obtained after 12 hours was released from the polyethylene tapper and left to stand in an atmosphere of 80 ° C. for 1 hour to obtain a soft resin foam (drying step). The skin layer of the obtained soft resin foam was cut to a specified thickness, and each measurement sample of the sound absorbing material was prepared (skin layer cutting step).

[Comparative Example 3]
Polymer A as the base resin (A), baking soda (sodium hydrogen carbonate) [FE-507 manufactured by Eiwa Kasei Kogyo Co., Ltd.], antioxidant [IRGASTAB PUR68 manufactured by BASF Japan], and carbon black [Asahi Carbon]. Asahi Thermal Co., Ltd.] was added in the amounts shown in Table 3 and mixed sufficiently to prepare a solution A. The amounts of salicylic acid [primary salicylic acid (pKa: 2.97) manufactured by Kishida Chemical Co., Ltd.], water (C), silanol condensation catalyst (D) [2-ethylacid phosphate (Johoku Chemical Industry Co., Ltd.), respectively, shown in Table 3 Co., Ltd., acidic phosphoric acid ester, JP-502)], and foam stabilizer [Ebonic Japan Co., Ltd., Tegostave B8123] were added and mixed thoroughly to prepare a solution B.
The obtained solutions A and B are foamed under the following mixing conditions using a two-component dispenser (Twinflow VR50 (manufactured by Tomita Engineering Co., Ltd.)) at a weight ratio of solution A: solution B = 2: 1. Body preparation was performed.
Dynamic mixer: 75cc 4 steps, 1700rpm
Static mixer: 24 elements, tip discharge diameter 8 mm
Discharge rate: Continuous mixing and discharging was performed at 1 shot (75 cc) / 2.4 seconds, the mixed solution was poured into a polyethylene mold, foamed with the upper lid set, and left for 12 hours. The working conditions were 23 ° C. (Foam molding step) The foamed cured product after 12 hours was released from the polyethylene mold and left to stand in an atmosphere of 90 ° C. for 12 hours to obtain a soft resin foam (drying step). The skin layer of the obtained soft resin foam was cut to a specified thickness, and each measurement sample was prepared (skin layer cutting step).

[Comparative Example 4]
Except for changing the amount of dicarbonate diester used, the amount of water (C) used, and the amount of silanol condensation catalyst (D) used to the amounts shown in Table 3, and changing the mixing amount to 214 g. , Each measurement sample of the sound absorbing material was obtained in the same manner as in Example 8.

[Comparative Example 5]
Not using the dicarbonate diester, changing the amount of water (C) used and the amount of silanol condensation catalyst (D) used to the amounts shown in Table 3, and changing the mixing amount to 1000 g. Other than that, each measurement sample of the sound absorbing material was obtained in the same manner as in Example 8.

[Comparative Examples 6 to 10]
In Comparative Example 6, glass wool (GW 64K, manufactured by Asahi Fiber Glass Co., Ltd.) was used as a measurement sample. In Comparative Example 7, polyurethane foam (Inoac F2, manufactured by Inoac Corporation) was used as a measurement sample. In Comparative Example 8, polyurethane foam (Inoac F9M, manufactured by Inoac Corporation) was used as a measurement sample. In Comparative Example 9, an ethylene propylene diene rubber foam (Eptsealer EV-1000, manufactured by Nitto Denko KK) was used as a measurement sample. In Comparative Example 10, Thinsulate (registered trademark) (manufactured by 3M, model number TAI 2047) was used as a measurement sample.

For the measurement samples of Examples 8, 9 and Comparative Examples 3 to 10, the shear modulus, the flow resistance per unit thickness, the density, the porosity, and the Young's modulus were measured by the above-mentioned methods. These values are shown in Table 3. In Example 9, the porosity and Young's modulus were not measured. In addition, Young's modulus was not measured for Comparative Examples 6 to 8.

Further, using a sample having a thickness of 10 mm as a measurement sample of Examples 8, 9 and Comparative Examples 3 to 10, vertical using an acoustic tube having an inner diameter of 40 mm at 20 ° C. in accordance with JIS A 1405-2. The incident sound absorption coefficient was measured. The sound absorbing material made of foam is in a state where the skin layer is completely cut.
The measurement results are shown in FIGS. 3 to 12.

* 4: DABCO as the silanol condensation catalyst (D) is DABCO NE1070, which acts as a foaming aid (E).

According to Table 3 and FIGS. 3 to 12, Examples 8 and 9 are made of foam having a shear modulus of 7,000 Pa or less and a flow resistance of 1,000,000 N · s / m ⁴ or more per unit thickness. It can be seen that the sound absorbing material absorbs sound well in a wide frequency range.
On the other hand, the sound absorbing material of Comparative Example 3 made of a foam having a shear modulus of 7,000 Pa or less but a flow resistance per unit thickness of less than 1,000,000 N · s / m ⁴ has a low frequency band of 650 Hz or more and 1000 Hz or less. The sound absorption characteristics were inferior.
Further, the sound absorbing material of Comparative Example 4 made of a foam having a flow resistance of 1000000 N · s / m ⁴ or more per unit thickness but a shear elastic modulus of more than 7000 Pa has a low frequency band of 650 Hz or more and 1000 Hz or less. The sound absorption characteristics in the above range were slightly inferior, and the sound absorption characteristics in the frequency range of 2000 Hz or more and 4000 Hz or more were inferior.
Further, the sound absorbing material of Comparative Example 5, which cannot be measured because the shear modulus is higher than a predetermined value and the flow resistance per unit thickness is excessively high, is inferior in sound absorbing characteristics at a frequency of 650 Hz or more and 4500 Hz or less.

Further, a sample having a thickness of 10 mm was prepared for the sound absorbing materials of Example 8, Example 9, Comparative Example 3, Comparative Example 4, Comparative Example 8 and Comparative Example 9 based on the above method. Using this sample, the vertical incident transmission loss was measured at frequencies of 1000 Hz to 4500 Hz, measured using an acoustic tube with an inner diameter of 40 mm according to ASTM E2611. The measurement results of the vertical incident transmission loss of these samples are shown in FIG.
According to FIGS. 3, 4, and 13, Examples 8 and 8 are made of a foam having a shear modulus of 7,000 Pa or less and a flow resistance of 1,000,000 N · s / m ⁴ or more per unit thickness. It can be seen that the sound absorbing material of No. 9 can achieve both good sound absorbing property and sound insulating property in a frequency band within a wide range.
According to FIGS. 5, 6, 10, 11, and 13, a comparative example 3 in which a shear modulus of 7,000 Pa or less and a flow resistance per unit thickness of 1,000,000 N · s / m ⁴ or more are not combined. It can be seen that the sound absorbing materials of Comparative Example 4, Comparative Example 8 and Comparative Example 9 cannot achieve both good sound absorption and sound insulation in a frequency band within a wide range.

Claims

A foam obtained by foaming and curing a base resin (A) having a reactive silicon group containing a polyoxyalkylene polymer (A1).
A foam having a sound absorption coefficient of 70% or more at a frequency of 1000 Hz to 5500 Hz, measured using a B tube at 20 ° C. using a sample having a thickness of 25 mm and in accordance with JIS A 1405-2.
The first aspect of the present invention, wherein the sound absorption coefficient measured by using a B tube at 20 ° C. in accordance with JIS A 1405-2 using a sample having a thickness of 25 mm is maximized in the frequency range of 1000 Hz to 1700 Hz. Foam.
The first or second claim, wherein the sound absorption coefficient at a frequency of 800 Hz, which is measured using a B tube at 20 ° C. using a sample having a thickness of 25 mm in accordance with JIS A 1405-2, is 40% or more. Foam.
A foam obtained by foaming and curing a foam resin composition containing the base resin (A) and a chemical foaming agent (B).
The foam according to any one of claims 1 to 3, wherein the content of the metal salt and / or inorganic particles in the foam is 2.5% by weight or less based on the weight of the foam.
The foam according to claim 4, wherein the chemical foaming agent (B) is a non-pyrolytic type.
The foam according to claim 4 or 5, wherein the chemical foaming agent (B) contains a dicarbonate diester (B-1).
The foam according to any one of claims 1 to 6, wherein the base resin (A) contains an acrylic resin (A2) having a glass transition temperature of 35 ° C. or higher.
The reactive silicon group is a trimethoxysilyl group, a (methoxymethyl) dimethoxysilyl group, the following formulas (1) to (3):

(In formulas (1) to (3), R 1 is an independently hydrocarbon group having 1 or more and 20 or less carbon atoms, and the hydrocarbon group as R 1 may be substituted. Further, it may have a hetero-containing group, X is a hydroxy group or a hydrolyzable group, a is 1, 2, or 3, and R 4 is a divalent linking group, which R 4 has. The two bonds are bonded to a carbon atom, an oxygen atom, a nitrogen atom, or a sulfur atom in the linking group, respectively, and R 2 and R 3 are independently hydrogen atoms and 1 or more carbon atoms, respectively. It is either an alkyl group having 20 or less, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a silyl group.)
The group represented by and the following formula (4):
-R 5- CH 2- Si (R 1 ) 3-a (X) a (4)
(In the formula (4), R 1, and a is the same as R 1, and a in equation (1) to (3), R 5 is a heteroatom.)
The foam according to any one of claims 1 to 7, which is a group selected from the group consisting of the groups represented by.
The foam according to any one of claims 1 to 8, which has a foaming ratio of 15 to 60 times.
The foam according to any one of claims 1 to 9, wherein the FP hardness at 0 ° C. is 60 or less.
It contains a base resin (A), a chemical foaming agent (B), and a silanol condensation catalyst (D).
The base resin (A) has a reactive silicon group and has
The base resin (A) contains a polyoxyalkylene polymer (A1) and an acrylic resin (A2) having a glass transition temperature of 35 ° C. or higher.
A resin that gives a foam having a sound absorption coefficient of 70% or more at frequencies of 1000 Hz to 5500 Hz, measured using a B tube at 20 ° C., in accordance with JIS A 1405-2, using a sample having a thickness of 25 mm. Composition.
The resin composition according to claim 11, wherein the base resin (A) has a branch in the main chain structure and has three or more ends.
A sound absorbing material comprising the foam according to any one of claims 1 to 10.
Shear modulus is 7000 Pa or less,
A sound absorbing material made of a foam having a flow resistance of 1000000 N · s / m 4 or more per unit thickness.
The sound absorbing material according to claim 14, which has a density of 100 kg / m 3 or less.
The sound absorbing material according to claim 14 or 15, wherein the foam comprises a composition containing a polyoxyalkylene polymer.
The sound absorbing material according to claim 16, wherein the foam is a cured product of a resin composition containing a polyoxyalkylene polymer (A1) having a reactive silicon group.
The 17th claim, wherein the foam comprises a cured product of a resin composition containing the oxyalkylene polymer (A1) having a reactive silicon group and an acrylic resin (A2) having a reactive silicon group. Sound absorbing material.
Any of claims 14 to 18, wherein the total of the content of the inorganic fine particles of the foam and the content of the metal atom contained in the foam as a metal salt in the foam is 2.5% by weight or less. The sound absorbing material according to item 1.
At a frequency of 650 Hz, a vertical incident sound absorption coefficient of 0.15 or more is shown as a vertical incident sound absorption coefficient measured using an acoustic tube having an inner diameter of 40 mm and a test piece having a thickness of 10 mm in accordance with JIS A1405-2. The sound absorbing material according to any one of claims 14 to 19, which exhibits a vertically incident sound absorbing coefficient of 0.4 or more at any frequency within a frequency range of 650 Hz or more and 1000 Hz or less.
The vertical incident sound absorption coefficient measured using an acoustic tube with an inner diameter of 40 mm and a test piece with a thickness of 10 mm in accordance with JIS A1405-2 in the frequency range of 1000 Hz or more and 4500 Hz or less is 0.45 or more. The sound absorbing material according to any one of claims 14 to 20.
The foam has a sound absorption coefficient of 70% or more at a frequency of 1000 Hz to 5500 Hz, which is measured using a B tube at 20 ° C. using a sample having a thickness of 25 mm and in accordance with JIS A 1405-2. The sound absorbing material according to claim 17 or 18.
The foam has a vertical incident transmission loss of 7 dB or more at a frequency of 1000 Hz to 4500 Hz, measured using a sample having a thickness of 10 mm and using an acoustic tube having an inner diameter of 40 mm according to ASTM E2611.
The sound absorbing material according to any one of claims 14 to 22, which has sound insulating properties.
A sound absorbing method for causing the sound absorbing material according to any one of claims 14 to 23 to absorb sound containing a component having a frequency in the range of 650 Hz or more and 4500 Hz or less.
The sound absorbing method according to claim 24, wherein the sound to be absorbed contains a component in the frequency range of 650 Hz or more and 1000 Hz or less.
A sound insulation method for insulating sound containing components in the frequency range of 1000 Hz to 4500 or less by using the sound absorbing material according to claim 23.
A sound absorbing structure comprising the sound absorbing material according to any one of claims 14 to 23 and a support supporting the sound absorbing material.
The sound absorbing structure according to claim 27, wherein the support is a pneumatic tire, and the sound absorbing material is supported by the tire so as to cover at least a part of a surface of the pneumatic tire on the lumen side.
The support comprises a motor and a casing that houses the motor.
The sound absorbing structure according to claim 27, wherein the gap between the motor and the casing is filled with a sound absorbing material.
A vehicle having the sound absorbing structure according to any one of claims 27 to 29.
A method for manufacturing a sound absorbing structure, comprising the sound absorbing material according to any one of claims 14 to 23 and a support supporting the sound absorbing material.
A method for manufacturing a sound absorbing structure, wherein the sound absorbing material is fixed to the surface of the support or the sound absorbing material is filled in a space defined by the support.
A liquid resin composition containing a polyoxyalkylene polymer (A1) having a reactive silicon group is applied to the surface of the support or filled in the space defined by the support. ,
By curing the resin composition while foaming to form a foam, the foam as a sound absorbing material is adhered to the surface of the support.
31. The method for manufacturing a sound absorbing structure according to claim 31.
The method for manufacturing a sound absorbing structure according to claim 32, wherein the liquid resin composition is applied to the inner surface of the tire as the support.
The method for manufacturing a sound absorbing structure according to claim 32, wherein in the support including the motor and the casing accommodating the motor, the gap between the motor and the casing is filled with the liquid resin composition.
Forming a formwork using a 3D printer
Injecting a liquid resin composition containing a polyoxyalkylene polymer (A1) having a reactive silicon group into the mold, and
The method for producing a sound absorbing material according to any one of claims 14 to 23, wherein the resin composition is cured while being foamed to form a foam.
A building provided with the sound absorbing material according to any one of claims 13 to 23.
A vehicle provided with the sound absorbing material according to any one of claims 13 to 23.