CN111601854B - Forming method and one-liquid room temperature moisture-curable reactive hot melt composition with fire resistance - Google Patents

Abstract

The present invention provides a method for forming a fire-resistant structure using a nonflammable material (or a fire-retardant material) and a one-pack room-temperature moisture-curable reactive hot-melt composition which is cured (solidified) after application and then cured by moisture in the air, and which has heat resistance and fire resistance; the present invention also provides a one-pack room temperature moisture curable reactive hot melt composition having sufficient storage stability and fire resistance. A method for forming a fire-resistant structure by using a one-pack room-temperature moisture-curable reactive hot-melt composition having fire resistance, wherein the one-pack room-temperature moisture-curable reactive hot-melt composition retains its shape at a temperature of less than 80 ℃ after moisture curing, the one-pack room-temperature moisture-curable reactive hot-melt composition after moisture curing has a temperature of 50 ℃ or higher when used, and the one-pack room-temperature moisture-curable reactive hot-melt composition is set to 180 ℃ or higher, whereby a heat curing reaction, a heat insulating layer forming reaction, and a flame retardant reaction of the one-pack room-temperature moisture-curable reactive hot-melt composition are caused to form the fire-resistant structure.

Description

Forming method and one-liquid room temperature moisture-curable reactive hot melt composition with fire resistance

Technical Field

The present invention relates to a method for forming and a one-pack room temperature moisture curable reactive hot melt composition having flame resistance. The present invention particularly relates to a method for forming a structure which is fast in curing and exhibits excellent heat resistance and flame resistance after curing, and a one-pack room temperature moisture curable reactive hot melt composition having flame resistance.

Background

Patent document 1 discloses a refractory structure of an attic partition wall, which includes an attic partition wall having a wall surface material and an elongated material formed of a section steel having a groove portion and provided through the wall surface material, wherein a hole portion through which the elongated material is inserted is formed in the wall surface material, a 1 st incombustible material for blocking the groove portion of the elongated material is provided at an insertion portion through which the elongated material is inserted into the hole portion, a 2 nd incombustible material for blocking a gap between an outer peripheral surface of the elongated material and an inner peripheral surface of the hole portion is provided, and the 2 nd incombustible material is formed of an amorphous sealing material filled in the gap.

As a composition constituting a flame-resistant amorphous sealing material, for example, patent document 2 discloses a curable composition for a flame-resistant structure containing, as essential components, (a) a (meth) acrylic polymer containing at least 1 crosslinkable silyl group in the molecule and having a crosslinkable silyl group at a molecular chain end, (B) a reactive organic polymer containing less than 1 crosslinkable silyl group in the molecule, and (C) unexpanded, heat-expandable hollow spheres, wherein 0.01 to less than 20 parts by weight of (C) is contained per 100 parts by weight of the total amount of (a) and (B), and 10 to 300 parts by weight of (B) is contained per 100 parts by weight of (a); the curable composition for a fire-resistant structure is characterized in that (C) unexpanded heat-expandable hollow spheres are expanded by heating when a cured product of the curable composition is exposed to flame, whereby the cured product forms a foamed heat-insulating layer. The curable composition for a refractory structure described in patent document 2 exhibits heat resistance and also exhibits fire resistance after curing.

Further, patent document 3 discloses an acrylic resin composition containing ase:Sub>A branched copolymer selected from branched copolymers having ase:Sub>A comb-type skeleton, branched copolymers having ase:Sub>A star-type skeleton, and (ase:Sub>A-B-ase:Sub>A) _n Type (D) block copolymer, and (A-B) _n 100 parts by weight of at least 1 thermoplastic acrylic copolymer, 20 to 200 parts by weight of the total amount of the phosphorus compound and the neutralized heat-expandable graphite, and 50 to 500 parts by weight of an inorganic filler; the weight ratio of the neutralized heat-expandable graphite to the phosphorus compound is 9 to 1. Wherein A represents a vinyl polymer block, and B represents a block copolymer comprising a copolymer represented by the formula CH ₂ (co) polymer block having a (meth) acrylate represented by = CR 'COOR "(wherein R' represents a hydrogen atom or a methyl group, and R" represents an alkyl group having 2 to 14 carbon atoms) as a structural unit. The acrylic resin composition described in patent document 3 has excellent flame resistance.

Documents of the prior art

Patent literature

Patent document 1: japanese patent laid-open publication No. 2017-082482

Patent document 2: japanese patent No. 4616572

Patent document 3: japanese unexamined patent publication No. 10-237263

Non-patent document

Non-patent document 1: soot (v) 6, flame iv (v) 6, tokyo fire hall, "125221248112454\\1241252124521245812412512363, 45 pool 12412363, attention: 12472347212434! (Note fire from lithium ion batteries!), [ only line ], average 28 years, 12 months, 22 days, tokyo fire department, [ average 29 years, retrieval at 10 months, 16 days ], internet < http:// www.tfd.method.tokyo.jp/hp.kouhouka/pdf/281222.pdf >, pdf

Disclosure of Invention

Problems to be solved by the invention

In buildings, electric/electronic products, and the like, there are parts where fire resistance is required. For example, in a lithium ion battery used in a smartphone, there is a case where a short circuit occurs between a positive electrode and a negative electrode in the battery to ignite clothes or the like as described in non-patent document 1, and therefore, it is required to prevent this and/or prevent ignition between battery cells (cells) when an overcurrent flows in the battery. Therefore, it is conceivable to use the curable composition for a refractory structural body as described in patent document 2.

However, the curable composition for a refractory structure described in patent document 2 is not applicable to the production of a structure having fire resistance with a short takt time, such as a refractory wall in a factory construction, because the setting time (curing time) of the curable composition for a refractory structure is long, and the workability is poor. In the production in factories, there is a demand for development of a gasket, a coating agent, a covering material, an adhesive material and/or an adhesive agent having a short setting time and fire resistance suitable for high-speed work.

The acrylic resin composition described in patent document 3 has excellent flame resistance, but is for injection molding (or extrusion molding). The standard conditions for injection molding are such that the resin ejection temperature is 210 ℃ or higher and 260 ℃ and the injection pressure is 80MPa or higher and 140MPa or lower. Therefore, it cannot be applied to Hot Melt (HM) construction in which the resin ejection temperature is about 80 ℃ to 150 ℃ inclusive and the injection pressure is about 0.3MPa to 5.0MPa inclusive. In addition, there is no heat-resistant hot melt composition having flame resistance at present. Therefore, there is a demand for a reactive hot-melt curable composition having flame resistance suitable for hot-melt application.

Accordingly, an object of the present invention is to provide a method for forming a fire-resistant structure using a nonflammable material (or a fire retardant material) and a one-pack room temperature moisture curable reactive hot melt composition which is cured (solidified) after application and then cured by moisture in the air, and which has heat resistance and fire resistance. Further, it is intended to provide a one-pack room temperature moisture curable reactive hot melt composition having sufficient storage stability (pot life) and having flame resistance.

Means for solving the problems

In order to achieve the above object, the present invention provides a method for forming a fire-resistant structure using a one-pack room temperature moisture-curable reactive hot melt composition having fire resistance, wherein the one-pack room temperature moisture-curable reactive hot melt composition maintains its shape at a temperature of less than 80 ℃ after moisture curing, the one-pack room temperature moisture-curable reactive hot melt composition after moisture curing is used at a temperature of 50 ℃ or higher, and the one-pack room temperature moisture-curable reactive hot melt composition is set to 180 ℃ or higher, thereby causing a thermal curing reaction, a heat insulating layer forming reaction, and a flame retardant reaction of the one-pack room temperature moisture-curable reactive hot melt composition to form the fire-resistant structure.

In order to achieve the above object, the present invention provides a one-pack room-temperature moisture-curable reactive hot melt composition having flame resistance, which comprises (a) an organic polymer having a moisture-curable group, (B) a high-temperature heat-curable flame retardant resin, (C) a thermal expansion agent, and (D) a flame retardant.

Effects of the invention

According to the forming method and the one-pack room temperature moisture-curable reactive hot melt composition having fire resistance of the present invention, there can be provided a method for forming a fire-resistant structure using a non-combustible material (or a fire-retardant material) and one-pack room temperature moisture-curable reactive hot melt composition which is cured (solidified) after application and then cured by moisture in the air, which has heat resistance and fire resistance; and a one-pack room temperature moisture-curable reactive hot melt composition having sufficient storage stability and flame resistance.

Drawings

Fig. 1 is a graph showing the results of differential scanning calorimetry of phenol-diaminodiphenylmethane-type benzoxazines.

Detailed Description

[ method of Forming refractory Structure ]

The forming method of the invention is as follows: a method for forming a fire-resistant structure by using a one-pack room-temperature moisture-curable reactive hot melt composition having fire resistance and a member such as a building member or an electric/electronic component. The method comprises the following steps: a method for forming a fire-resistant structure, which comprises using a non-combustible or fire-resistant member and a one-pack room-temperature moisture-curable reactive hot-melt composition having fire resistance to form a fire-resistant structure.

The "incombustible" member refers to, for example, a member produced from a material suitable as an incombustible material according to item 9 of japanese building standard law 2 in the case where the member is a building member, and a member for other electric/electronic component applications or the like, which does not substantially generate heat even when heated in a normal atmosphere. The "flame-retardant" component is, for example, a component produced from a quasi-incombustible material and a flame-retardant material specified in item 5 and item 6 of article 1 of the japanese building standard act, and is a component having a characteristic of HB or more in the UL94 (Underwriters Laboratories inc.) standard in terms of a component and/or a resin component for other electrical/electronic component applications, and the like, in the case where the component is a building component. In the present invention, "flame resistance" means flame resistance and/or flame retardancy that meets the standards for flame retardancy such as UL94 standard. In the present invention, the term "fire-resistant structure" refers to a structure having fire resistance and/or fire retardancy, and also refers to a structure made of a noncombustible material, a quasi-noncombustible material, and/or a fire-retardant material, which complies with the building standards. When the flame-retardant structure is a structure having flame retardancy, the flame-retardant structure includes a structure formed by using a material that meets the flame retardancy standard such as UL94 standard.

Here, the one-pack room temperature moisture curable reactive hot melt composition of the present invention has the following characteristics: moisture curing occurs at normal temperature and the shape is maintained below 80 ℃ after moisture curing. That is, the one-pack room-temperature moisture-curable reactive hot melt composition exhibits heat resistance at a normal application temperature (from room temperature to about 80 ℃) after moisture curing.

The temperature at which the one-pack room-temperature moisture-curable reactive hot melt composition after moisture curing is used is 50 ℃ or higher, preferably 80 ℃ or higher and 150 ℃ or lower. In the present invention, the "at the time of use" of the one-liquid room temperature moisture curable reactive hot melt composition means, for example, when the one-liquid room temperature moisture curable reactive hot melt composition is applied to a predetermined portion, when the one-liquid room temperature moisture curable reactive hot melt composition is filled in a predetermined injection container, or when the predetermined portion is coated. In the one-pack room temperature moisture-curable reactive hot melt composition (i.e., the cured product of the one-pack room temperature moisture-curable reactive hot melt composition) of the present invention, the temperature is set to a high temperature of 180 ℃ or higher, whereby a heat curing reaction of the one-pack room temperature moisture-curable reactive hot melt composition, a heat insulating layer forming reaction by thermal expansion, and a flame retardant reaction by a gas phase and/or a solid phase are caused.

That is, the one-pack room temperature moisture curable reactive hot melt composition of the present invention has the following characteristics: the hot melt composition can be used under conditions in the case of Hot Melt (HM) application (the temperature of the hot melt composition is 50 ℃ or more, and preferably 80 ℃ or more and 150 ℃ or less, and the injection pressure is 0.3MPa or more and 5.0MPa or less, hereinafter, sometimes referred to as "conditions of use for HM application"), and does not cause a thermosetting reaction, a reaction for forming a heat insulating layer, and a reaction for imparting flame retardancy under the conditions of use for HM application.

Therefore, the method for forming a refractory structure of the present invention includes the steps of: the method for manufacturing the heat-curable hot melt adhesive includes a step of applying or filling a one-pack room temperature moisture-curable reactive hot melt composition having flame resistance to a predetermined portion of a predetermined member, and a step of moisture-curing the one-pack room temperature moisture-curable reactive hot melt composition at room temperature by using moisture in the air after the step. When the one-pack room temperature moisture-curable reactive hot melt composition cured by moisture becomes a high temperature of 180 ℃ or higher (for example, when exposed to flame and/or when a site covered with a cured product of the one-pack room temperature moisture-curable reactive hot melt composition becomes a high temperature of 180 ℃ or higher), the heat curing reaction is initiated, the heat insulating layer is formed by the heat insulating layer forming reaction, and the flame retardant reaction is performed. Thereby, a refractory structure is formed.

Here, the conventional hot melt composition needs to contain a resin skeleton that melts at a high temperature. Therefore, in the conventional hot melt composition, even if a cross-linked structure is formed in the molecular structure, the resin skeleton melted at a high temperature is melted at a high temperature of 180 ℃ or higher, and the melt drips (melt 12489125221248312503. On the other hand, the one-pack room temperature moisture curable reactive hot melt composition of the present invention can suppress the occurrence of melt dripping because a cured product thereof undergoes a thermosetting reaction at a high temperature of 180 ℃ or higher.

The "fire-resistant structure" in the present invention refers to a structure including structural members such as building parts, automobile parts, electric/electronic parts, and fiber/leather/clothing parts. Moreover, the refractory structure is: the structure is obtained by bringing an amorphous seal ring, a gasket, a potting agent, a coating agent, or an adhesive (reactive hot melt having flame resistance) (hereinafter, these may be referred to as "members having flame resistance") having flame resistance into contact with, filling, and/or coating a portion of the constituent members which requires flame resistance, a portion which requires flame spread prevention, or the like. Examples of the refractory structure include: a structure obtained by bonding refractory members to each other with a member having fire resistance, a structure obtained by coating a terminal of a secondary battery with a member having fire resistance, a structure obtained by coating a lead of a speaker with a member having fire resistance, or the like, a structure obtained by coating a portion of an electric/electronic component or the like, which is required to suppress ignition, or the like.

For example, in a refractory structure in which a terminal of a secondary battery is covered with a member having fire resistance, when an abnormal current flows in the secondary battery due to a short circuit or the like between a positive electrode and a negative electrode, burning between battery cells can be prevented. In addition, in the fire-resistant structure in which the lead of the speaker is covered with a member having fire resistance, ignition and ignition in the case where an overcurrent flows through the lead can be prevented.

In the present invention, "fire resistance (or fire resistance)" mainly means: the characteristics of extinguishing the combustion of the member and preventing the delay of combustion by forming a heat insulating layer. The flame resistance can be evaluated by, for example, a test of the UL94 standard. The "fire-resistant member" includes a member having incombustibility (incombustible material), a member having fire retardancy (fire-retardant material), and a quasi-fire-resistant structure having a certain fire resistance without having complete fire resistance. However, in the case of using a member having fire resistance as the covering material, a general material formed of a predetermined resin material is included in the flame retardant material.

(example 1 of method for Forming refractory Structure)

As the fire-resistant structure, there is a structure obtained by using a fire-resistant member on a random mat (CIPG) of a small portable electronic device. For example, a small portable electronic device is configured by joining one flame-retardant housing member and the other flame-retardant housing member to each other. In this case, the refractory structure is produced through the following steps: the method for manufacturing the small portable electronic device includes a step of preparing a one-pack room temperature moisture curable reactive hot melt composition having fire resistance, a step of applying the one-pack room temperature moisture curable reactive hot melt composition in an uncured state to a portion to be sealed of one case member of the small portable electronic device, a step of placing a portion to be joined to the one case member of the other case member on the portion to be sealed of the one case member in an opposed manner and pressure-bonding the portion, and a step of curing the uncured one-pack room temperature moisture curable reactive hot melt composition.

(example 2 of method for Forming refractory Structure)

As the fire-resistant structure, a structure in which a lead of a cone speaker is covered with a fire-resistant member is exemplified. As an example, the cone speaker includes a bobbin (coil bobbin), a voice coil (voice coil), a lead wire (horizontal line), a cone (cone), and an edge portion. The bobbin has a cylindrical shape, and a voice coil is wound around an outer wall thereof. The voice coil is opposed to the annular magnet with a predetermined gap. The cone functions as a vibration plate, and the end portion is fixed to the frame portion via the edge portion of the cone. In addition, a silk thread is arranged on the cone. One end of the lead wire is connected with the lead wire on the cone, and the other end of the lead wire is connected with the external terminal. An electrical signal is supplied from an amplifier or the like to an external terminal via a speaker cable. In this case, the lead wires and/or the nylon wires on the cone are covered with a one-pack room temperature moisture curable reactive hot melt composition having fire resistance, and cured to manufacture a cone speaker as a fire resistant structure. Thus, even if gas is generated by heat generation of the voice coil and the gas is ignited, the lead wire or the like is prevented from being burnt.

[ one-pack room temperature moisture-curable reactive hot melt composition having flame resistance ]

The one-pack room-temperature moisture-curable reactive hot melt composition of the present invention comprises: a composition which cures rapidly after application to an adherend and exhibits heat resistance and flame resistance (i.e., shape retention performance) after curing. That is, the one-pack room temperature moisture curable reactive hot melt composition having flame resistance comprises: an organic polymer having a moisture-curable group (A) which exhibits heat resistance by moisture curing, a high-temperature heat-curable flame-retardant resin (B) which becomes a highly heat-resistant resin by heat curing and exhibits flame resistance, a thermal expansion agent (C) which thermally expands by combustion, and a flame retardant (D). More specifically, the one-pack room-temperature moisture-curable reactive hot melt composition having flame resistance comprises (A) a solid organic polymer having a moisture-curable group, (B) a high-temperature heat-curable flame-retardant resin having a heat curing temperature of 180 ℃ or higher, (C) a thermal expansion agent having a thermal expansion temperature of 180 ℃ or higher, and (D) a flame retardant having a temperature at which a flame-retardant reaction occurs of 180 ℃ or higher. The one-pack room temperature moisture curable reactive hot melt composition having flame resistance may further comprise (E) an aminosilane for imparting adhesiveness. The "thermal expansion temperature" refers to a temperature at which the thermal expansion agent expands.

[ (A) organic Polymer having moisture-curable group ]

(A) The organic polymer having a moisture-curable group (hereinafter, sometimes referred to as a "(a) component") is an organic polymer having a moisture-curable group and being solid at ordinary temperature. Examples of the moisture-curable group include an isocyanate group and a crosslinkable silicon group.

Examples of the organic polymer having a moisture-curable group include a urethane prepolymer having an isocyanate group, and an organic polymer having a crosslinkable silicon group. From the viewpoint of lowering the solid-state temperature of the cured composition, the glass transition temperature is preferably-30 ℃ or higher, more preferably-20 ℃ or higher, and still more preferably-10 ℃ or higher. In addition, the glass transition temperature is 50 ℃ or lower, preferably 20 ℃ or lower, more preferably 10 ℃ or lower, and still more preferably 0 ℃ or lower, from the viewpoint that the cured composition has flexibility.

As the urethane prepolymer having an isocyanate group, for example, a compound obtained by reacting a polyol with a polyisocyanate can be used. As the polyol, polyether polyol, crystalline polyester polyol, amorphous polyester polyol, acrylic polyol, polycarbonate polyol, polybutadiene polyol, dimer diol (dimer diol), and the like can be used. These polyols may be used alone or in combination of two or more. As the polyol, polyether polyol, crystalline polyester polyol, amorphous polyester polyol, and acrylic polyol are preferably used.

Examples of the organic polymer having a crosslinkable silicon group include a crosslinkable silicon group-containing (meth) acrylate polymer and a crosslinkable silicon group-containing urethane prepolymer.

(crosslinkable silicon group-containing (meth) acrylate Polymer)

The crosslinkable silyl group in the acrylic ester polymer having a crosslinkable silyl group and having a glass transition temperature of-20 ℃ or higher and 50 ℃ or lower (hereinafter, sometimes referred to as "crosslinkable silyl group-containing (meth) acrylic ester polymer") as the component (a) has a hydroxyl group and/or a hydrolyzable group bonded to a silicon atom, and can be crosslinked by a silanol condensation reaction. The crosslinkable silicon group is exemplified by a crosslinkable silicon group represented by formula (1).

[ solution 1]

In the formula, R ¹ Represents an alkyl group having 1 to 20 carbon atoms, a substituted alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, wherein 2 or more R's are present ¹ In this case, they may be the same or different. X represents a hydrolyzable group, and when 2 or more X's are present, they may be the same or different. a represents 0, 1, 2, or 3.

In the crosslinkable silicon group of formula (1), a is preferably 2 or 3. In the case where a is 3, the curing speed becomes higher than that in the case where a is 2.

As the above-mentioned R ¹ Specific examples thereof include alkyl groups such as methyl and ethyl, substituted alkyl groups such as methoxymethyl, and cycloalkyl groups such as cyclohexyl. Among them, methyl is preferred.

The hydrolyzable group represented by X is not particularly limited, and any hydrolyzable group known in the art may be used. The alkoxy group is preferable in terms of mild hydrolyzability and easy handling. Among the alkoxy groups, an alkoxy group having a small number of carbon atoms has high reactivity, and the reactivity decreases as the number of carbon atoms increases, as in the order of methoxy > ethoxy > propoxy. It may be selected according to purpose and/or use, but a methoxy group and/or an ethoxy group is generally used. In the case of the crosslinkable silyl group represented by formula (1), a is preferably 2 or more in view of curability.

Specific examples of the crosslinkable silyl group include a trialkoxysilyl group (-Si (OR) such as trimethoxysilyl group OR triethoxysilyl group ² ) ₃ ) (ii) a Dialkoxysilyl group (-SiR) such as methyldimethoxysilyl group and methyldiethoxysilyl group ¹ (OR ² ) ₂ ). Where R is ¹ Same as above, R ² Is methyl and/or ethylAlkyl groups such as phenyl. The crosslinkable silyl group is preferably a trimethoxysilyl group or a triethoxysilyl group, and more preferably a trimethoxysilyl group, from the viewpoint of high reactivity. From the viewpoint of obtaining a cured product having flexibility, a methyldimethoxysilyl group or a methyldiethoxysilyl group is preferable.

The crosslinkable silyl group may be used singly or in combination of two or more. The crosslinkable silyl group is present in the main chain or in the side chain, or in both the main chain and the side chain.

At least 1 crosslinkable silicon group, preferably 1.1 to 5 crosslinkable silicon groups, are present on average in the molecule of the polymer 1. When the number of crosslinkable silicon groups contained in the molecule is less than 1, curability becomes insufficient, and when too much, the mesh structure becomes too dense, and thus good mechanical properties are not exhibited.

The (meth) acrylate polymer is a polymer having a repeating unit represented by the general formula (2).

-CH ₂ C(R ³ )(COOR ⁴ )- (2)

In the formula (2), R ³ Represents a hydrogen atom or a methyl group, R ⁴ Represents a hydrocarbon group which may have a substituent. The polymer may be a homopolymer or a copolymer. The term (meth) acrylate refers to acrylate and/or alkyl methacrylate.

As the monomer to be a repeating unit, an alkyl (meth) acrylate is preferable. As examples of the alkyl (meth) acrylate compound, conventionally known compounds are listed. Examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, and stearyl (meth) acrylate.

The hydrocarbon group such as an alkyl group of the (meth) acrylate may have a substituent such as a hydroxyl group, an alkoxy group, a halogen atom, or an epoxy group. Examples of such a compound include (meth) acrylates having a hydroxyl group such as hydroxyethyl (meth) acrylate, and (meth) acrylates having an alkoxy group such as methoxyethyl (meth) acrylate, and (meth) acrylates having an amino group such as (meth) acrylates having an epoxy group such as glycidyl (meth) acrylate, and diethylaminoethyl (meth) acrylate. An unsaturated compound having a polymer chain (macromonomer)) such as an acrylate having a polystyrene chain or the like may also be used.

The (meth) acrylate polymer of component (a) may further contain a repeating unit derived from a compound copolymerizable with the (meth) acrylate compound in addition to the repeating unit derived from the (meth) acrylate compound. Examples of the compound copolymerizable with the (meth) acrylic acid ester compound include acrylic acid such as (meth) acrylic acid, amide compounds such as (meth) acrylamide, vinyl ether compounds such as alkyl vinyl ether, and other compounds such as acrylonitrile, styrene, α -methylstyrene, vinyl chloride and vinyl acetate.

The crosslinkable silicon group may be introduced into the (meth) acrylate polymer of the component (A) by a known method. Examples of the method for introducing the crosslinkable silyl group include the following methods.

(1) Copolymerizing an unsaturated compound having a crosslinkable silicon group.

(2) Polymerization is carried out using an initiator and/or a chain transfer agent having a crosslinkable silicon group.

(3) The (meth) acrylate polymer having a functional group such as a hydroxyl group is reacted with a compound having a crosslinkable silicon group and another functional group reactive with the functional group such as epoxysilane.

As a method for introducing the crosslinkable silyl group, (1) a method of copolymerizing an unsaturated compound having a crosslinkable silyl group is preferable from the viewpoint that the crosslinkable silyl group can be easily introduced.

(unsaturated Compound having crosslinkable silicon group)

The unsaturated compound having a crosslinkable silicon group is preferably an alkyl (meth) acrylate having a crosslinkable silicon group and/or a vinyl silane. Examples of such compounds include gamma- (meth) acryloyloxypropylalkoxysilane such as gamma- (meth) acryloyloxypropyltrimethoxysilane, gamma- (meth) acryloyloxypropylmethyldimethoxysilane or gamma- (meth) acryloyloxypropyltriethoxysilane, and vinylalkoxysilane such as vinyltriethoxysilane. Among them, alkyl (meth) acrylates having crosslinkable silicon groups and substituted alkyl groups having an alkyl group with 10 or less, preferably 3 or less carbon atoms are preferable. The amount of the crosslinkable silyl group-containing unsaturated compound used is preferably an amount such that the crosslinkable silyl group is contained in an average of 1.1 to 5, preferably 1.1 to 3 groups per molecule of the polymer of the component (a).

(glass transition temperature of crosslinkable silicon group-containing (meth) acrylate Polymer)

The crosslinkable silicon group-containing (meth) acrylate polymer has a glass transition temperature (hereinafter, also referred to as "Tg") of-20 ℃ or higher and 50 ℃ or lower. Preferably a glass transition temperature of-10 ℃ or more and 40 ℃ or less, more preferably a glass transition temperature of-10 ℃ or more and 30 ℃ or less. When the glass transition temperature is less than-20 ℃, the adhesive strength immediately after the adhesion tends to be poor. Further, when the glass transition temperature exceeds 50 ℃, the melt viscosity (melt viscosity) becomes high, and the application of the one-pack room-temperature moisture-curable reactive hot melt composition to an adherend tends to be difficult. The glass transition temperature can be easily estimated by using the Fox equation depending on the kind and/or amount of the monomer component.

The molecular weight of the crosslinkable silyl group-containing (meth) acrylate polymer as the component (a) is preferably 3,000 to 50,000 in terms of number average molecular weight (molecular weight in terms of polystyrene measured by GPC), more preferably 5,000 to 30,000, and still more preferably 6,000 to 15,000. When the number average molecular weight is 3,000 or less, the initial adhesion after coating is low, and when it is 50,000 or more, the viscosity during coating operation becomes too high, and workability is deteriorated. The polymer of component (A) is preferably solid at room temperature or has a ring and ball softening point of preferably 80 ℃ or higher.

(polymerization method)

As the polymerization method, a radical polymerization method can be used. For example, a general solution polymerization method and/or a bulk polymerization method using a thermal polymerization initiator such as benzoyl peroxide or azobisisobutyronitrile can be used. Further, a method of polymerizing by irradiating light or radiation using a photopolymerization initiator can also be used. In the radical copolymerization, a chain transfer agent such as lauryl mercaptan and/or 3-mercaptopropyltrimethoxysilane may be used for the purpose of adjusting the molecular weight. The polymer of the component (A) of the present invention can be easily obtained by a general radical polymerization method using a thermal polymerization initiator and by such a method. Other polymerization methods such as living radical polymerization described in Japanese patent application laid-open No. 2000-086998 may be used.

The monomer other than the crosslinkable silyl group-containing monomer used in the polymer of the component (a) of the present invention is preferably an alkyl (meth) acrylate, more preferably an alkyl (meth) acrylate having an alkyl group with 1 to 30 carbon atoms, and particularly preferably an alkyl (meth) acrylate having an alkyl group with 1 to 30 carbon atoms and having no substituent. The polymer of the component (a) of the present invention is preferably in a solid state or a state having substantially no fluidity at room temperature because it is used for hot melting. In particular, in order to obtain a polymer having a glass transition temperature of-20 ℃ or higher and 50 ℃ or lower, it is preferable to use methyl methacrylate (the Tg of the polymer is 105 ℃) and an alkyl (meth) acrylate having 2 to 30 carbon atoms in the alkyl group and having no substituent, in particular, an alkyl acrylate, as the monomer, from the viewpoints of ease of production and cost. Further, from the viewpoint of ease of production and cost, methyl methacrylate and butyl acrylate (polymer having a Tg of-55 ℃) are particularly preferably used. When methyl methacrylate is used, the amount of the repeating unit derived from methyl methacrylate in the polymer of the component (a) is preferably 20% by mass or more, and more preferably 30% by mass or more.

(ratio of monomers used)

The preferable monomer used in the polymer of the component (a) is preferably used so as to be 50% by mass or more, preferably 70% by mass or more, more preferably 80% by mass or more, particularly preferably 90% by mass or more, and further 95% by mass or more in the polymer of the component (a). In particular, alkyl acrylates having an alkyl group of 2 to 30 carbon atoms and having no substituent, such as methyl methacrylate and butyl acrylate, are preferably used in the above-mentioned amount. In addition, as the monomer used in the polymer of the component (a), a macromonomer can be used, but in the case of using, it is preferably used so that the amount of the macromonomer in the polymer of the component (a) is 10 mass% or less, further 5 mass% or less, and particularly 3 mass% or less.

[ (B) high-temperature thermosetting flame-retardant resin ]

By blending (B) a high-temperature thermosetting flame retardant resin (hereinafter, sometimes referred to as "component (B)") into a reactive hot melt having flame resistance, when the cured product is exposed to flame, thermosetting is performed at 180 ℃ or higher, so that the cured product is prevented from melting and dripping and/or running out, and an excellent carbonized layer having flame resistance is formed. Since the (meth) acrylate polymer is melted and dropped before forming a flame retardant layer under high temperature conditions of 180 ℃ or the like, it is required to contain the component (B) of the present invention in one-pack room-temperature moisture-curable reactive hot melt composition. Thus, the melting and dropping resistance can be maintained even under high temperature conditions such as in the case of firing, and the airtightness of the refractory structure can be maintained by forming the carbonized coating layer. The thermosetting temperature is a temperature at which curing is started.

(B) The high-temperature heat-curable flame retardant resin is a resin that is heat-cured at high temperature. Because of high flame retardancy, a novolac (novolak) type phenol resin, a thermosetting melamine resin (methylolmelamine), an epoxy resin, and a resin having a dihydrobenzoxazine ring (hereinafter, referred to as "oxazine ring-containing resin") are preferable. These resins are not likely to undergo a curing reaction at a normal use temperature of 70 to 120 ℃ of one-pack room-temperature moisture-curable reactive hot melt composition, and can ensure a sufficient storage stability period. The reaction proceeds at a temperature not higher than the decomposition temperature of the component (a), and flame resistance (shape retention performance) is imparted. In addition, since these resins are mainly composed of a resin having an aromatic ring structure, hydrogen is less than that of a resin having an aliphatic structure. Therefore, since it is hard to burn and easy to carbonize, it has high fire resistance and high shape retention performance. That is, in the case where the one-pack room temperature moisture-curable reactive hot melt composition contains a resin having a cyclic structure such as an aromatic ring structure as the component (B), when a thermal curing reaction is performed at a high temperature of 180 ℃ or higher, the amount of carbon char generated (CR value) due to the cyclic structure is high, and therefore, a heat-insulating layer (carbonized layer) is easily formed and the fire resistance is improved.

Further, as the (B) component, an oxazine ring-containing resin is preferable because toxic gases such as formaldehyde are not generated upon curing. When an organic polymer having a crosslinkable silicon group is used as the (a) organic polymer having a moisture-curable group and aminosilane is used as the adhesiveness imparting agent, the epoxy resin and the (E) aminosilane react with each other, and the storage stability (the time from the melting of the one-pack room-temperature moisture-curable reactive hot melt composition to the application) is shortened, and therefore, it is preferable not to use the epoxy resin from the viewpoint of the storage stability.

The amount of the high-temperature-curable flame-retardant resin (B) to be added is preferably 1 part by weight or more, more preferably 2 parts by weight or more, and most preferably 5 parts by weight or more, per 100 parts by weight of the component (a), from the viewpoint of satisfactory flame resistance. From the viewpoint of obtaining good curing properties of the one-pack room-temperature moisture-curable reactive hot melt composition, it is preferably less than 150 parts by weight, more preferably less than 100 parts by weight, and most preferably less than 80 parts by weight.

[ resin having a dihydrobenzoxazine ring ]

Since the resin having a dihydrobenzoxazine ring is subjected to ring-opening polymerization at about 210 ℃, a coating layer can be formed and sintered before the dropping temperature (240 ℃ to 265 ℃) is reached.

The resin having a dihydrobenzoxazine ring is disclosed in, for example, jp-a-49-47387, and can be synthesized from a corresponding compound having a phenolic hydroxyl group, formalin, and a primary amine according to the following formula (3). In this resin, a ring-opening polymerization reaction is initiated by heating, and a crosslinked structure having excellent characteristics is formed without generating volatile components.

[ solution 2]

In the formula (3), R represents an alkyl group, a substituted alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or the like.

Examples of the compound having a phenolic hydroxyl group include a bisphenol compound, a biphenol (biphenol) compound, a triphenol compound, and a tetraphenol compound. Examples of the phenol resin (phenolic resin) include phenol resins such as novolac resin, resol resin (resol resin), phenol-modified xylene resin, alkyl phenol resin, melamine phenol resin, and polybutadiene-modified phenol resin. Examples of the bisphenol compound include bisphenol a, bisphenol S, bisphenol F and positional isomers thereof, and tetrafluorobisphenol a. When a phenol resin is used, a heat-resistant resin containing a dihydrobenzoxazine ring contains a structural unit represented by the following general formula (a) and a structural unit represented by the following general formula (B), a/B is 1/0.25 to 9 in terms of a molar ratio, and when the structural units are directly bonded or bonded via an organic group, a cured product excellent in strength and heat resistance can be obtained.

[ solution 3]

[ solution 4]

And, R ⁵ The aromatic hydrogen in the structural units (a) and (B) may be substituted with an arbitrary substituent by removing one hydrogen in the ortho position to the hydroxyl group of the structural unit (a). Each knotThe number of structural units is not particularly limited, but when the number of structural units (A) contained in 1 molecule is m and the number of structural units (B) is n, m.gtoreq.1, n.gtoreq.1, and m + n.gtoreq.2, preferably 10. Gtoreq.m + n.gtoreq.3 may be used. The structural units may be bonded directly or through an organic group. Examples of the organic group include an alkylene group and a xylylene group, and examples of the alkylene group include a long-chain alkylene group having 5 or more carbon atoms. Specific examples of the primary amine include methylamine, cyclohexylamine, aniline, and substituted aniline.

The high-temperature heat-curable flame-retardant resin (B) can be synthesized by adding a mixture of a compound having a hydroxyl group and a primary amine to an aldehyde heated at 70 ℃ or higher, reacting the mixture at 70 to 110 ℃, preferably 90 to 100 ℃ for 20 to 120 minutes, and then drying the reaction product at 120 ℃ or lower under reduced pressure.

Further, a resin having a dihydrobenzoxazine ring obtained by reacting a monophenol compound such as phenol or a polyphenol such as a bisphenol compound with a polyvalent primary amine such as diaminodiphenylmethane with an aldehyde can also be used. Specifically, a resin having a dihydrobenzoxazine ring obtained by reacting a dihydric phenol compound and a diamine compound with an aldehyde as described in WO2011/125665 can be used. The resin having a dihydrobenzoxazine ring obtained by using an aromatic amine such as diaminodiphenylmethane has a high thermosetting temperature, and therefore, when the resin is used in a one-pack room-temperature moisture-curable reactive hot melt having flame resistance (50 ℃ or higher, or 80 to 150 ℃), a thermosetting reaction is not easily caused, and a sufficiently long storage stability period can be obtained, and therefore, the resin can be preferably used.

[ phenol resin ]

As the phenol resin, a phenol novolac resin may be used. The novolac resin includes phenol novolac resin and/or bisphenol novolac resin, phenol-modified xylene resin, alkyl novolac resin, and the like. The phenolic resin is a component which reacts with (C) the thermal expansion agent to form a cured product having a durable structure. The resol resin is not preferable because it can be cured alone and the storage stability period (120 ℃ C.) is shortened.

When the amount of the phenol resin added is less than 3 parts by weight based on 100 parts by weight of the resin having a dihydrobenzoxazine ring, it becomes difficult to improve curability. When the amount exceeds 70 parts by weight, curability is not easily improved, and mechanical properties may be deteriorated. By setting the amount of the phenol resin to 3 to 70 parts by weight, curability can be improved without degrading various properties such as mechanical properties.

[ (C) thermal expansion agent ]

The thermal expansion agent (C) of the present invention is: a compound which does not foam at the temperature (50 ℃ or higher, or 80 ℃ or higher and 150 ℃ or lower) at the time of use, and foams at a temperature of 180 ℃ or higher when a cured product of a one-pack room-temperature moisture-curable reactive hot-melt composition is exposed to flame, thereby forming a flame-resistant and heat-insulating layer. As the thermal expansion agent (C), there are a solid compound and a liquid compound. In the one-pack room-temperature moisture-curable reactive hot melt composition having a high use temperature, it is preferable to use a compound (C) which is solid at room temperature (23 ℃) and has a low vapor pressure at the use temperature (50 ℃ or higher, or 80 ℃ or higher and 150 ℃ or lower) and generates little harmful gas. The thermal expansion agent (C) (hereinafter, may be referred to as "component (C)") is not particularly limited as long as it is a particle capable of expanding the one-pack room-temperature moisture-curable reactive hot melt composition of the present invention. Examples of the component (C) include thermally expandable graphite, aluminum phosphite, unexpanded microspheres, unexpanded vermiculite, and unexpanded perlite. The heat-expandable graphite, aluminum phosphite, and unexpanded microspheres are preferred, and the heat-expandable graphite and aluminum phosphite are more preferred. When a gap is formed by the combustion of the one-pack room-temperature moisture-curable reactive hot melt composition, the component (C) exerts a function of maintaining the shape (a flame-retardant function) by filling the gap through thermal expansion.

(thermal expansion graphite)

The thermally expandable graphite is a conventionally known substance that expands when heated, and starts to expand when heated at 200 to 220 ℃. The expansion ratio is not particularly limited, but is preferably 10 to 600 times, more preferably 50 to 500 times, and still more preferably 100 to 300 times. The use of expanded graphite having an expansion ratio of 10 or more improves the fire resistance of the obtained composition. Further, by using expanded graphite having an expansion ratio of 600 times or less, a foamed heat insulating layer which is less likely to be broken when a cured product is exposed to flame is formed.

The thermally expandable graphite is one of crystalline compounds that maintain a layered structure of carbon and are obtained by treating powders of natural graphite flakes, pyrolytic graphite, kish graphite (Kish graphite), and the like with an inorganic acid such as concentrated sulfuric acid, nitric acid, and selenic acid, and a strong oxidizing agent such as concentrated nitric acid, perchloric acid, perchlorate, permanganate, dichromate, and hydrogen peroxide to generate a graphite intercalation compound. The thermally expandable graphite obtained by the acid treatment as described above may be further neutralized with ammonia, an aliphatic lower amine, an alkali metal compound, an alkaline earth metal compound, or the like.

The average particle size of the thermally expandable graphite is not particularly limited, but is preferably 0.1 μm or more and 1000 μm or less, and more preferably 25 μm or more and 1000 μm or less. If the average particle size is less than 0.1. Mu.m, the workability of the composition during application may be deteriorated, and if the average particle size exceeds 1000. Mu.m, the appearance of the surface of the composition may be problematic.

Examples of commercially available products of the thermally expandable graphite include "GREP-EG" manufactured by Tosoh corporation and "GRAFGUARD" manufactured by GRAFTECH corporation.

The amount of the thermally expandable graphite to be added is preferably less than 60 parts by weight, more preferably less than 50 parts by weight, and most preferably less than 40 parts by weight, based on 100 parts by weight of the total amount of the components (a) and (B), from the viewpoint of forming an appropriate foamed heat insulating layer when exposed to flame. From the viewpoint of exhibiting good flame resistance, it is preferably 5 parts by weight or more, more preferably 10 parts by weight or more, and most preferably 20 parts by weight or more.

(unexpanded microspheres)

Unexpanded microspheres are conventionally known substances that expand when heated, and begin to expand when heated to 180 ℃ to 300 ℃. The foaming ratio when the unfoamed state is 100% is preferably 150 to 2000%, more preferably 300 to 1500%, and still more preferably 700 to 800%. The use of the unexpanded microspheres having an expansion ratio of 150% or more improves the flame resistance of the obtained composition. Further, by using 2000% or less of unexpanded microspheres, a foamed heat insulating layer that is less likely to be broken when a cured product is exposed to flame is formed.

The unexpanded microsphere has a shell made of a thermoplastic resin such as vinylidene chloride/acrylonitrile copolymer, methyl methacrylate/acrylonitrile copolymer, and methacrylonitrile/acrylonitrile copolymer, and contains a volatile substance therein and expands by heat. The volatile substance contained in the gas-phase refrigerant may be a hydrocarbon such as butane or isobutane, and the expansion initiation temperature may be changed by selecting the type of the volatile substance. From the viewpoint of thermal expansion occurring at an appropriate timing, the expansion start temperature is preferably 180 ℃ or higher, more preferably 200 ℃ or higher, and still more preferably 220 ℃ or higher. From the viewpoint of sufficient flame resistance, it is preferably 300 ℃ or lower, more preferably 290 ℃ or lower, and still more preferably 280 ℃ or lower.

The particle diameter of the unexpanded microspheres is preferably 1 to 50 μm, more preferably 5 to 40 μm, and still more preferably 10 to 30 μm. When the particle diameter is less than 1 μm, sufficient foaming cannot be obtained, and when it exceeds 50 μm, the microspheres are easily broken.

The unexpanded microspheres preferably have a film thickness (thickness of the outer shell) of 2 to 15 μm. As the unexpanded microspheres, for example, "Matsumoto Microsphere F series" (manufactured by Songbu oil & fat pharmaceuticals), or "Expancel series" (manufactured by Expancel corporation), which are commercially available, can be used.

The amount of the unexpanded microspheres added is preferably less than 20 parts by weight, more preferably less than 15 parts by weight, and most preferably less than 10 parts by weight, based on 100 parts by weight of the total amount of the components (a) and (B), from the viewpoint of forming a suitable foamed thermal insulating layer when exposed to flame. From the viewpoint of exhibiting good flame resistance, it is preferably 0.01 parts by weight or more, more preferably 0.1 parts by weight or more, and most preferably 1 part by weight or more.

(aluminum phosphite)

Aluminum phosphite is a crystalline, white fine powder containing phosphorus and aluminum, which is hardly soluble in water. The aluminum phosphite is decomposed and foamed at 380-480 ℃. Changes to aluminum metaphosphate [ Al (PO) when heated ₃ ) ₃ ]And aluminum orthophosphate [ AlPO ] ₄ ]The volume of the expandable porous material before heating is about 30 to 40 times that of the expandable porous material before heating.

The aluminum phosphite used in the present invention is preferably spherical. The term "spherical" as used herein means a spherical or approximately spherical shape having a diameter distribution in the range of about 2 to 125 μm and an average diameter of about 20 μm. Examples of the aluminum phosphite used in the present invention include aluminum phosphites described in japanese patent No. 2899916.

The aluminum phosphite described above has excellent flowability and high mechanical strength as compared with an amorphous shape. Therefore, as long as the above-mentioned aluminum phosphite is used, the following effects can be obtained: the workability such as mixing work in producing a one-pack room temperature moisture-curable reactive hot melt composition is improved, the workability in coating the composition is improved, the flame retardant effect of the composition is improved, and the like.

The amount of the aluminum phosphite added is preferably less than 60 parts by weight, more preferably less than 50 parts by weight, and most preferably less than 40 parts by weight, based on 100 parts by weight of the total amount of the components (a) and (B), from the viewpoint of forming an appropriate foamed heat insulating layer when exposed to flame. From the viewpoint of exhibiting good flame resistance, it is preferably 5 parts by weight or more, more preferably 10 parts by weight or more, and most preferably 20 parts by weight or more.

[ (D) flame retardant ]

The flame retardant of the invention is: a flame retardant which hardly causes a flame-retardant reaction at a temperature (50 ℃ or higher, or 80 ℃ or higher and 150 ℃ or lower) during use and which is less susceptible to adverse effects caused by the flame-retardant reaction. In addition, the flame retardant of the present invention is: a flame retardant which does not shorten the storage stability period in practice and which is flame-retarded by a flame-retarding reaction mechanism when a one-pack room-temperature moisture-curable reactive hot-melt cured product is exposed to flame.

The flame retardant (hereinafter, sometimes referred to as the "component (D)") is not particularly limited, and conventionally known compounds can be used. Examples of the component (D) include metal hydroxides such as aluminum hydroxide, halogen flame retardants such as chlorine compounds and bromine compounds, phosphorus flame retardants such as condensed phosphoric acid esters, antimony flame retardants such as antimony trioxide and antimony pentoxide, phosphorus compounds such as triphenyl phosphoric acid esters and ammonium polyphosphates, phosphazene flame retardants, inorganic oxides such as silica fillers, and hydrous layered silicates such as kaolinite. These flame retardants may be used alone or in combination of 2 or more.

(mechanism of flame retardancy)

Here, a mechanism of a flame-retardant reaction (flame-retardant mechanism) by the component (D) is explained. The mechanism of flame retardancy of a flame retardant differs depending on the type of the flame retardant. The mechanism of the flame-retardant reaction obtained based on the type of a typical flame retardant is shown below.

< mechanism of flame-retarding reaction in gas phase >

(1) Based on a mechanism of a flame-retardant reaction of a halogen compound and antimony trioxide

When a compound containing a halogen element is burned, it is gasified during combustion, and active OH radicals are trapped as in the following (a). This stabilizes the active OH radicals by the capture effect of the active OH radicals. Further, carbonization by dehydrogenation (dehydrocarbonization effect) generates hydrogen halide which is nonflammable, and thus, it also exhibits an oxygen blocking effect to thereby achieve flame retardancy.

(a)·OH+HX→H ₂ O + X (X: halogen; free radical)

X + RH → HX + R (R: alkyl)

It is considered that SbX is generated as shown in the following (b) in the flame retardant reaction between the halogen compound and antimony trioxide ₃ And/or SbOX, sbX ₃ And/or SbOX exhibits a radical trapping effect and/or an air blocking effect in a gas phase, thereby imparting flame retardancy.

(b)Sb ₂ O ₃ +2HX→2SbOX+H ₂ O

5SbOX→Sb ₄ O ₅ X ₂ +SbX ₃

4Sb ₄ O ₅ X ₂ →5Sb ₃ O ₄ X+SbX ₃

3Sb ₃ O ₄ X→4Sb ₂ O ₃ +SbX ₃

(2) Mechanism of flame-retardant reaction by phosphorus compound

As shown in the following (c), the active OH radicals are stabilized by the radical trapping effect of phosphoric acid, thereby providing flame retardancy.

(c)H ₃ PO ₄ →HPO ₂ +PO+etc

H+PO→HPO

H+HPO→H ₂ +PO

·OH+PO→HPO+O

(3) Mechanism of flame-retardant reaction based on metal hydroxide (hydrated metalate)

When the hydrated metal compound is combusted, the following effects are exhibited: a cooling effect by an endothermic reaction of dehydration at the time of combustion, a dilution effect of combustion gas in a gas phase by generated water, and a thermal insulation effect of generated oxides and generated carbon coke. These effects are utilized to achieve flame retardancy. The reaction formula of aluminum hydroxide and magnesium hydroxide is shown below as an example.

Al(OH) ₃ →Al ₂ O ₃ +H ₂ O (about 200 ℃ C.)

Mg(OH) ₂ →MgO+H ₂ O (about 340 ℃ C.)

< mechanism of flame-retardant reaction in solid phase >

In the solid phase, the carbon char (carbonized layer) and the carbon char and inorganic heat insulating layer are made flame retardant by the generation promoting effect and stabilizing effect. When the organic compound is thermally decomposed, carbon in the organic compound is changed to CO and/or CO as long as oxygen is sufficiently present ₂ . However, when oxygen is insufficient, a carbonized solid is formed, and the structure thereof isA heat insulating layer, a carbonized layer.

For example, red phosphorus is made flame retardant by generating condensed phosphoric acid by oxidation of red phosphorus and binding with moisture.

In addition, as for the phosphorus compound, phosphoric acid is produced by oxidation at a high temperature, metaphosphoric acid is produced, and polymetaphosphoric acid is produced. These phosphoric acid layers formed as a nonvolatile protective layer showed an air-blocking effect. Further, the strong dehydration action of these phosphoric acids promotes the formation of carbon char, thereby also exhibiting an air-blocking effect (dehydration carbonization promoting effect). These effects are utilized to achieve flame retardancy.

Further, a flame retarding mechanism based on the following is exemplified: the inorganic-carbon coke complex is generated by using the hydrated metal compound and the flame retardant auxiliary agent. In this case, the composite of the metal compound of the combustion product and the carbon char (metal oxide + borate glass layer + carbon char) is stabilized to retard the destruction of the heat-insulating layer during combustion, thereby achieving flame retardancy.

In addition, a mechanism of flame retardancy based on a silicone resin (silicone) compound-based flame retardant is exemplified. In the case of this situation, it is, by using-Si-O-in combustion residues the formation of a composite layer of the-Si-C-compound and the carbon char results in flame retardancy.

Further, as a mechanism of the flame-retardant reaction in the solid phase, the following mechanism is also exemplified: the phosphorus compound and the N-containing compound produce a carbon char foam, which exhibits a heat insulating effect and an oxygen heat insulating effect, thereby imparting flame retardancy. When the phosphorus compound and the N-containing compound are used in combination, the ratio of the foaming component (N-containing compound: used as a foaming agent for a foam rubber) increases, and the phosphorus compound and the N-containing compound can also function as the thermal expansion agent as the component (C).

For example, APP (ammonium polyphosphate) and PER (pentaerythritol) are used in combination to produce a foamed carbon char (foamed layer) to make the composition flame retardant. In this case, when the heat insulating layer is formed using APP and PER in combination, the heat insulating layer exhibits excellent heat insulating effect and oxygen blocking effect in an extremely thin layer because the outside temperature is low under the flame retardant condition.

Here, since the outside temperature is low (i.e., the combustion time is short in seconds) under the flame-retardant condition, the flame-retardant effect is high even with an extremely thin heat-insulating layer when exposed to a flame in a short time. On the other hand, since the outside temperature is high (i.e., the burning time is long in hours) under fire resistance conditions, a thick heat insulating layer is required in the case of long-term exposure to flame. For example, in the above-mentioned foamed coke, the external temperature for continuing the combustion of the heat insulating layer having a foamed layer on the surface thereof is 347 ℃, 747 ℃ at 0.1cm, 1500 ℃ at 0.27cm and 4500 ℃ at 1.0cm when the thickness of the heat insulating layer is 0.01cm, and thus it is found that the above-mentioned foamed coke functions as an excellent heat insulating layer.

Synergistic effects based on the combination of gas and solid phase systems

By using the mechanism of the flame-retardant reaction in the gas phase and the mechanism of the flame-retardant reaction in the solid phase together, a synergistic effect is obtained. For example, the synergistic effect of phosphorus and halogen is enumerated. That is, a halogen having an effect on a gas phase and phosphorus having an effect on a solid phase are used in combination, whereby an excellent flame retardant effect is exhibited. That is, the phosphorus halide and the oxyhalide are generated to exhibit a radical trapping effect and to provide flame retardancy.

Among the flame retardants, aluminum hydroxide and phosphazene flame retardants are preferable because of their high flame retardant effect, and aluminum hydroxide is preferable from the viewpoint of not generating harmful gas, and the like. The phosphazene flame retardant is preferable from the viewpoint of melting at the temperature at which the one-pack room-temperature moisture-curable reactive hot melt composition is applied, that is, the temperature of the coating resin, and reducing the viscosity at the time of coating.

The amount of the flame retardant to be added is preferably less than 100 parts by weight, more preferably less than 80 parts by weight, and most preferably less than 60 parts by weight, based on 100 parts by weight of the total amount of the components (a) and (B), from the viewpoint of achieving a balance between cured physical properties and coatability when used and flame retardancy when exposed to flame. From the viewpoint of exhibiting good flame retardancy, the amount of the flame retardant is preferably 10 parts by weight or more, more preferably 20 parts by weight or more, and most preferably 30 parts by weight or more.

(Metal hydroxide)

The amount of the metal hydroxide to be added is preferably less than 100 parts by weight, more preferably less than 80 parts by weight, and most preferably less than 60 parts by weight, based on 100 parts by weight of the total amount of the components (a) and (B), from the viewpoint of achieving a balance between cured physical properties and coatability when used and flame retardancy when exposed to flame. From the viewpoint of exhibiting good flame retardancy, the amount of the flame retardant is preferably 10 parts by weight or more, more preferably 20 parts by weight or more, and most preferably 30 parts by weight or more.

(phosphazene flame retardant)

Phosphazene flame retardants are used as highly efficient phosphorus flame retardants because they can suppress a decrease in heat resistance of a resin composition due to the addition of a flame retardant, as compared with phosphate flame retardants. The phosphazene flame retardant is an organic compound having a-P = N-bond in a molecule, and preferable examples of the phosphazene flame retardant include a cyclic phosphazene compound represented by the following general formula (4), a chain phosphazene compound represented by the following general formula (5), and a crosslinked phosphazene compound in which at least one phosphazene compound selected from the group consisting of the following general formula (4) and the following general formula (5) is crosslinked by a crosslinking group. The cross-linked phosphazene compound is preferably a compound formed by cross-linking with a cross-linking group represented by the following general formula (6) from the viewpoint of flame retardancy.

[ solution 5]

In the formula (4), m is an integer of 3 to 25, R ⁶ Which may be the same or different, represent an aryl or alkylaryl group.

[ solution 6]

In the formula (5), N is an integer of 3 to 10,000, and Z represents-N = P (OR) ⁶ ) ₃ OR-N = P (O) OR ⁶ Y represents-P (OR) ⁶ ) ₄ Radical, OR-P (O) (OR) ⁶ ) ₂ And (4) a base. R ⁶ Which may be the same or different, represent an aryl or alkylaryl group.

[ solution 7]

In the formula (6), A is-C (CH) ₃ ) ₂ -、-SO ₂ -, -S-, or-O-, l is 0 or 1.

The cyclic and/or chain phosphazene compound represented by the general formula (4) and the general formula (5) is preferably R ⁶ A C6-20 aryl group which may be substituted with an alkyl group having 1-6 carbon atoms. Specifically, the following are listed: r is ⁶ Cyclic or chain phosphazene compounds which are aryl groups such as phenyl groups; r ⁶ A cyclic or chain phenoxyphosphazene which is an aryl group having 6 to 20 carbon atoms and substituted with an alkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, such as a tolyl group (o-, m-, p-tolyl group) or a xylyl group (2, 3-, 2,6-, 3, 5-xylyl group); or the R is ⁶ A combination of cyclic or chain phenoxyphosphazenes.

As the cyclic phosphazene compound represented by the general formula (4), R is particularly preferable ⁶ A cyclic phenoxyphosphazene which is a phenyl group. The cyclic phenoxyphosphazene compound is preferably a compound in which m in the general formula (4) is an integer of 3 to 8, and may be a mixture of compounds in which m is different. Specifically, hexaphenoxycyclotriphosphazene (a compound with m = 3), octaphenoxycyclotetraphosphazene (a compound with m = 4), decaphenoxycyclopentaphosphazene (a compound with m = 5), and the like, or a mixture thereof are exemplified. Among these compounds, a mixture of compounds in which m =3 is 50 mass% or more, m =4 is 10 to 40 mass%, and m =5 or more is 30 mass% or less is preferable.

The chain phosphazene compound represented by the general formula (5) is particularly preferably R ⁶ A chain phenoxyphosphazene which is a phenyl group. In the linear phenoxyphosphazene compound, n in the general formula (5) is preferably 3 to 1,000, more preferably 3 to 100, and still more preferably 3 to 25.

In the present invention, the phosphazene-based flame retardant is preferably at least 1 selected from the group consisting of a cyclic phenoxyphosphazene compound represented by general formula (4) and a crosslinked phenoxyphosphazene compound in which the cyclic phenoxyphosphazene compound represented by general formula (4) is crosslinked by a crosslinking group, from the viewpoint of flame retardancy and mechanical properties. Examples of commercially available phosphazene flame retardants include cyclic phenoxyphosphazenes such as "Rabile FP-110" and "Rabile FP-110T" manufactured by pharmaceutical companies and "SPS100" manufactured by Otsuka chemical companies.

The amount of the phosphazene flame retardant to be added is preferably less than 100 parts by weight, more preferably less than 80 parts by weight, and most preferably less than 60 parts by weight, based on 100 parts by weight of the total amount of the components (a) and (B), from the viewpoint of achieving a balance between cured physical properties and coatability during use and flame retardancy during exposure to flame. From the viewpoint of exhibiting good flame retardancy, the amount of the flame retardant is preferably 10 parts by weight or more, more preferably 20 parts by weight or more, and most preferably 30 parts by weight or more.

[ (E) aminosilane ]

The crosslinkable silyl group in the compound having a crosslinkable silyl group and an amino group (i.e., (E) aminosilane, hereinafter, also referred to as "component (E)") has a hydroxyl group and/or a hydrolyzable group bonded to a silicon atom and is a group crosslinkable by a silanol condensation reaction, as described for the component (a). Aminosilane is used as an adhesion imparting agent and also functions as a curing catalyst. As the amino group, a primary to tertiary amino group can be used.

Examples of aminosilanes include γ -aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldiethoxysilane and N-phenyl- γ -aminopropyltrimethoxysilane. In addition, derivatives such as reactants of these aminosilane compounds with epoxy compounds and/or acrylate compounds may also be used.

Among them, a compound having a molecular weight of 250 or more, such as a reaction product of an N-phenyl- γ -aminopropylmethyldimethoxysilane and/or an aminosilane compound with an epoxy compound and/or an acrylate compound, and a hydrolysis condensate of ethyltriethoxysilane (molecular weight: 192) and 3- [ N- (2-aminoethyl) amino ] propyltriethoxysilane (molecular weight: 250), is preferable because it is less likely to volatilize when the one-pack room-temperature moisture-curable reactive hot melt composition is melted, and a compound having a molecular weight of 400 or more is more preferable, and a compound having a molecular weight of 500 or more is more preferable. That is, a high molecular weight aminosilane that does not volatilize at high temperatures during use is preferable. Further, a compound having a secondary amino group is preferable because it undergoes a curing reaction when the one-pack room-temperature moisture-curable reactive hot melt composition is melted, does not easily become highly viscous, and undergoes a curing reaction after bonding.

The aminosilane may be used alone or in combination of two or more. The amount of the aminosilane to be used is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and particularly preferably 1 to 5 parts by mass, based on 100 parts by mass of the component (a). When the amount is less than 0.01 part by mass, the effect of imparting adhesiveness and/or the effect as a curing catalyst are insufficient, while when the amount is more than 20 parts by mass, the effect as a catalyst is not significant and is economically unfavorable.

[ silanol condensing catalyst ]

As the silanol condensing catalyst, for example, titanates such as tetrabutyl titanate and titanium tetraacetylacetonate; organotin compounds such as dibutyltin dilaurate, dioctyltin dineodecanoate, dioctyltin diacetone and tin octylate; zirconium compounds such as zirconium tetraacetylacetonate; aluminum compounds such as aluminum isopropoxide, aluminum triacetylacetonate and aluminum bis (ethylacetoacetate) monoacetylacetonate; bismuth compounds such as versatic acid (versatic acid) bismuth; amine compounds such as octylamine, xylylenediamine, 2,4, 6-tris (dimethylaminomethyl) phenol, morpholine, 1, 3-diazabicyclo (5, 4, 6) undec-7-ene, and carboxylic acid salts thereof; a reactant or a mixture of an amine compound such as a reactant or a mixture of laurylamine and tin octylate and an organotin compound; a low molecular weight polyamide resin obtained from an excess of polyamine and a polyacid; one or more kinds of known silanol catalysts such as a reaction product of an excess amount of polyamine and an epoxy compound.

The one-pack room-temperature moisture-curable reactive hot melt composition is usually applied to an adherend in a molten state at a high temperature of about 100 ℃. Thus, when a silanol condensation catalyst having high activity is used, a curing reaction proceeds during melting, and the viscosity becomes high, which may make the coating operation difficult. When one or two or more compounds selected from the group consisting of an organotin compound having an alkyl group having 5 or more carbon atoms, an aluminum compound, a bismuth compound and a titanium compound are used among the above curing catalysts, the silanol condensation catalysts are preferably used because the viscosity of the one-pack room-temperature moisture-curable reactive hot melt composition can be prevented from being increased at high temperatures. The amount of the silanol condensing catalyst to be used is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the (meth) acrylate polymer of the component (a).

[ other additives ]

In the one-pack room temperature moisture curable reactive hot melt composition of the present invention, other additives may be used in combination as required. Examples of such additives include liquid polymer compounds, crosslinkable silyl group-containing polymers other than component (a), tackifier resins, adhesiveness imparting agents other than aminosilanes, fillers, diluents, stabilizers, flame retardants, curability adjusting agents, radical inhibitors, metal deactivators, ozone deterioration inhibitors, phosphorus-based peroxide decomposers, slip agents, pigments, foaming agents, and mildewproofing agents. These additives may be used alone or in combination of two or more.

(liquid Polymer)

The liquid polymer compound which is liquid at room temperature has an effect of reducing the viscosity of the one-pack room-temperature moisture-curable reactive hot melt composition at the time of melting. Further, the liquid polymer compound has an effect of prolonging the open time (time for which bonding can be performed, time for which bonding can be performed after applying one-liquid room-temperature moisture-curable reactive hot melt composition). The viscosity of the liquid polymer compound at room temperature (B-type viscometer) is preferably 100Pa · s or less, more preferably 50Pa · s or less, and particularly preferably 20Pa · s or less. The liquid polymer compound may have a crosslinkable silyl group.

Examples of the main chain skeleton of the liquid polymer compound include polyoxyalkylene polymers such as polyoxypropylene, polyoxytetramethylene, and polyoxyethylene-polyoxypropylene copolymers; hydrocarbon polymers such as ethylene-propylene copolymers, polyisobutylene, polyisoprene, polybutadiene, and hydrogenated polyolefin polymers obtained by hydrogenating these polyolefin polymers; polyester polymers obtained by condensation of a dibasic acid such as adipic acid with a diol or ring-opening polymerization of lactones; a (meth) acrylate polymer obtained by radical polymerization of monomers such as ethyl (meth) acrylate and butyl (meth) acrylate; vinyl polymers obtained by radical polymerization of monomers such as (meth) acrylate monomers, vinyl acetate, acrylonitrile, and styrene; a graft polymer obtained by polymerizing a vinyl monomer in an organic polymer; a polysulfide polymer; a polyamide-based polymer; a polycarbonate-series polymer; diallyl phthalate polymers and the like. These skeletons may be composed of two or more kinds, either in blocks or randomly. Among these polymers, polyoxyalkylene polymers and/or (meth) acrylate polymers are preferable because they are easy to handle and have a large effect of extending the open time.

When a liquid polymer compound is excessively used, the properties of the one-pack room-temperature moisture-curable reactive hot melt composition such as heat resistance may be impaired. Accordingly, the content of the liquid polymer compound is preferably 0 to 100 parts by mass, more preferably 0 to 60 parts by mass, and still more preferably 0 to 30 parts by mass, relative to 100 parts by mass of the component (a).

(Polymer (solid) having crosslinkable silyl group other than component (A))

Examples of the polymer having a crosslinkable silyl group other than the component (A) and not in a liquid state include the crosslinkable silyl group-containing polymers disclosed in Japanese patent application laid-open No. H05-320608. In the present invention, the crosslinkable silicon group-containing polymer is sufficient only with the component (a). Accordingly, the content of the polymer having a crosslinkable silicon group other than the component (a) is preferably 0 to 100 parts by mass, more preferably 0 to 60 parts by mass, and still more preferably 0 to 30 parts by mass, based on 100 parts by mass of the component (a).

(tackifying resin)

Examples of the tackifier resin include terpene resins, aromatic modified terpene resins, hydrogenated terpene resins obtained by hydrogenation thereof, terpene-phenol resins obtained by copolymerization of terpenes and phenols, phenol resins, modified phenol resins, xylene-phenol resins, cyclopentadiene-phenol resins, coumarone-indene resins, rosin ester resins, hydrogenated rosin ester resins, xylene resins, low-molecular-weight polystyrene resins, styrene copolymer resins, styrene block copolymers, hydrogenated products of styrene block copolymers, petroleum resins (e.g., C5 hydrocarbon resins, C9 hydrocarbon resins, C5C9 hydrocarbon copolymer resins, etc.), hydrogenated petroleum resins, and DCPD resins. These may be used alone or in combination of two or more.

Examples of the styrene-based block copolymer and hydrogenated product thereof include a styrene-butadiene-styrene block copolymer (SBS), a styrene-isoprene-styrene block copolymer (SIS), a styrene-ethylene butylene-styrene block copolymer (SEBS), a styrene-ethylene propylene-styrene block copolymer (SEPS), a styrene-isobutylene-styrene block copolymer (SIBS), and the like.

The tackifier resin may be added in an amount of 0 to 500 parts by mass, 0 to 300 parts by mass, or 0 to 100 parts by mass based on 100 parts by mass of the component (A). In the present invention, the crosslinkable silyl group-containing polymer is sufficiently obtained only by the component (a), and when a tackifier resin is used, the properties of the one-pack room-temperature moisture-curable reactive hot melt composition such as heat resistance may be impaired. From this viewpoint, the content of the tackifier resin may be less than 0 to 10 parts by mass, preferably 0 to 5 parts by mass, and particularly preferably 0 to 3 parts by mass, relative to 100 parts by mass of the component (a).

(adhesion-imparting agent other than aminosilane)

Examples of the adhesiveness-imparting agent other than aminosilane include mercapto group-containing silanes such as γ -mercaptopropyltrimethoxysilane; epoxy-containing silanes such as gamma-glycidoxypropyltrimethoxysilane; silanes containing a vinyl-type unsaturated group such as vinyltrimethoxysilane; and silanes containing an isocyanate group such as γ -isocyanatopropyltrimethoxysilane. These silane coupling agents may be used alone or in combination of two or more.

(Filler)

Examples of the filler include calcium carbonate, magnesium carbonate, titanium oxide, carbon black, fused silica, precipitated silica, diatomaceous earth, white clay, kaolin, clay, talc, wood powder, walnut shell powder, rice hull powder, anhydrous silicic acid, quartz powder, aluminum powder, zinc powder, asbestos, glass fiber, carbon fiber, glass bead, alumina, glass microsphere (glass balloon), white sand balloon (shirasu balloon), silica microsphere (silica balloon), calcium oxide, magnesium oxide, silica and other inorganic fillers and/or pulp (pulp), wood filler such as wood wool chip, powder rubber, reclaimed rubber, thermoplastic or thermosetting resin fine powder, and polyethylene hollow body and other organic fillers. The filler may be used alone or in combination of two or more.

(Diluent)

The physical properties such as viscosity can be adjusted by adding a diluent to one-pack room temperature moisture-curable reactive hot melt composition. Examples of the diluent include phthalic acid esters such as dioctyl phthalate and diisodecyl phthalate; aliphatic dibasic acid esters such as dimethyl adipate and dioctyl adipate; polyethers such as polypropylene glycol and/or derivatives thereof; oils such as vinyl polymers, paraffin process oils (process oils) and naphthenic oils obtained by polymerizing vinyl monomers by various methods; synthetic waxes such as fischer-tropsch wax, polyethylene wax, polypropylene wax, and atactic polypropylene; petroleum waxes such as paraffin wax (paraffin wax) and microcrystalline wax. These diluents may be used alone or in combination of two or more.

(stabilizers)

Examples of the stabilizer include an antioxidant, a light stabilizer, and an ultraviolet absorber. When an antioxidant is used, the weather resistance and heat resistance of the cured product can be improved. Examples of the antioxidant include hindered phenol type, monophenol type, bisphenol type, and polyphenol type, and particularly preferred is hindered phenol type. When a light stabilizer is used, photooxidation degradation of the cured product can be prevented. Examples of the light stabilizer include benzotriazole compounds, hindered amine compounds, and benzoate compounds, and particularly hindered amine compounds are preferable. When an ultraviolet absorber is used, the surface weather resistance of the cured product can be improved. Examples of the ultraviolet absorber include benzophenone-based, benzotriazole-based, salicylate-based, substituted toluene-based, and metal chelate-based compounds, and benzotriazole-based compounds are particularly preferable. It is also preferable to use a phenolic and/or hindered phenolic antioxidant together with a hindered amine light stabilizer and a benzotriazole ultraviolet absorber.

In the one-pack room temperature moisture-curable reactive hot melt composition of the present invention, the total amount of the components (a), (B), and (C) is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more in the one-pack room temperature moisture-curable reactive hot melt composition, from the viewpoint of the characteristics of the one-pack room temperature moisture-curable reactive hot melt composition.

[ preparation of one-pack ambient temperature moisture-curable reactive Hot melt composition ]

The one-pack room-temperature moisture-curable reactive hot melt composition of the present invention can be prepared as a one-pack type, in which all the components to be mixed are stored in advance in a sealed state, and after application, the composition is cured by moisture in the air; it may be prepared in a two-component type, that is, a curing agent is separately compounded with a component such as a curing catalyst in advance, and the compounded material is mixed with the polymer composition before use.

The method for producing the one-pack room temperature moisture curable reactive hot melt composition of the present invention is not particularly limited, and a general method can be used, for example, a method of mixing the above components, kneading the mixture at room temperature or under heating using a mixer, roll, kneader or the like, or a method of dissolving and mixing the components using a small amount of an appropriate solvent.

The one-pack room-temperature moisture-curable reactive hot melt composition of the present invention preferably has a viscosity of 1Pa · s or more and 500Pa · s or less when used, and preferably has a viscosity of 100Pa · s or less at 80 ℃. When the viscosity at 80 ℃ exceeds 100 pas, the coating property and/or workability are deteriorated, or coating at a higher temperature is required to ensure the coating property and/or workability. In this case, the use range is limited, for example, the use on a substrate having low heat resistance becomes difficult. Therefore, the viscosity of the one-pack room-temperature moisture-curable reactive hot melt composition at 80 ℃ is more preferably 50 pas or less.

[ use ]

The one-pack room temperature moisture curable reactive hot melt composition of the present invention can be preferably used in production lines for construction, automobiles, electric/electronic, fiber/leather/clothing applications, bookbinding, and the like. That is, in these fields, there can be provided products having a cured product of the one-pack room-temperature moisture-curable reactive hot melt composition of the present invention. Further, the use of a heating gun (hand gun) or the like is also preferable for use in construction sites, DIY, and other facilities. Further, the one-pack room temperature moisture curable reactive hot melt composition of the present invention can be used as a sealant. In particular, the composition is useful for applications requiring flame resistance, and is useful as an adhesive, an adhesive material, a coating material, a potting material, or the like having flame resistance. In addition, a refractory structure can be formed by using a combination of a refractory sealing material containing the one-pack room-temperature moisture-curable reactive hot melt composition of the present invention as an active ingredient and a refractory wall material. Further, the one-pack room-temperature moisture-curable reactive hot melt composition of the present invention can be used for products requiring flame resistance.

The most widely used reactive hot melt adhesive is a urethane-based reactive hot melt adhesive. Here, in the case where one or both of the adherends are wood materials such as wood, plywood, or wood fiberboard, and/or moisture-permeable materials such as paper, from the viewpoint of suppressing a decrease in the time-course property of the adhesive strength, one of the organic polymers having a crosslinkable silicon group is preferable as compared with the urethane-based reactive hot melt adhesive. It is particularly preferable to use an organic polymer having a crosslinkable silicon group in a high-humidity atmosphere. That is, when a one-pack room temperature moisture curable reactive hot melt composition is used in place of the urethane reactive hot melt adhesive, deterioration of the adhesive strength over time can be more effectively prevented. Therefore, the one-pack room-temperature moisture-curable reactive hot melt composition of the present invention is particularly useful when the moisture-permeable material as described above is used as an adherend.

(effects of the embodiment)

The one-pack room temperature moisture-curable reactive hot melt composition of the present invention comprises component (a) which exhibits heat resistance by moisture curing, component (B) which becomes a highly heat-resistant resin by heat curing and exhibits flame resistance (shape retention), component (C) which exhibits flame resistance (shape retention) by filling in a gap generated by combustion through thermal expansion when exposed to high temperatures, and component (D) which exhibits flame retardancy, and therefore has the effects of being cured quickly, exhibiting heat resistance after curing, exhibiting flame resistance, and having good storage stability.

In addition, the one-pack room temperature moisture curable reactive hot melt composition of the present invention can be immediately transferred to the next step after passing through the solidification step (set process) by solid state even when the solidification time of the on-site production line is short. Further, the one-pack room temperature moisture-curable reactive hot melt composition of the present invention can be used as a hot melt composition having heat resistance because it is cured by moisture at room temperature without melting, and can be used in an environment of medium to high temperature (about 80 ℃).

Examples

The following examples are provided to explain the present invention more specifically. It should be noted that these examples are by no means illustrative and should not be construed as limiting.

Synthesis example 1 Synthesis of acrylic Polymer

Butyl acetate as a solvent was charged into a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen gas inlet tube, and a dropping funnel, and the temperature was raised to 110 ℃ while introducing nitrogen gas. Thereafter, gamma-methacryloxypropyltrimethoxysilane, methyl methacrylate, n-butyl acrylate, and n-stearyl acrylate were added. A solution of 2,2' -azobis (2-methylbutyronitrile) in butyl acetate is then added dropwise and the polymerization is carried out. After completion of the dropwise addition, the mixture was aged at 110 ℃ for 2 hours, cooled, and butyl acetate was added to the resin solution to obtain an acrylic polymer. The number average molecular weight (molecular weight in terms of polystyrene measured by GPC) of the obtained acrylic polymer was 10,000, and the glass transition temperature was 5 ℃.

TABLE 1

In table 1, the unit of the compounded amount of each compounded substance is "g". The details of the compounding agent are as follows. The acrylic polymer synthesized in the above synthesis example 1 was used as the component (a).

(component (B): high-temperature thermosetting flame-retardant resin)

A benzoxazine represented by the following formula (7) (P-d type, phenol-diaminodiphenylmethane type benzoxazine, manufactured by Siguo Kasei Kogyo Co., ltd.)

[ solution 8]

Fig. 1 shows Differential Scanning Calorimetry (DSC) data of the benzoxazine represented by formula (7). The DSC measurement was carried out by sealing the sample in an aluminum container (cell) (measurement conditions: under a nitrogen atmosphere). In fig. 1, the horizontal axis represents the cell temperature (deg.c) and the vertical axis represents the heat flow (mW).

(B') component: a thermosetting flame-retardant resin)

Resol-type phenolic resin

(component (C): thermal expansion agent)

FN260SD (unexpanded microspheres; manufactured by Songban oil pharmaceutical Co., ltd.)

APA-100 (spherical and foaming aluminum phosphite, manufactured by Taiping chemical industry Co., ltd.)

(component (D): flame retardant)

SPB-100 (phosphazene: crosslinked phenoxyphosphazene compound, compound obtained by crosslinking a cyclic phenoxyphosphazene represented by general formula (4) (mixture of general formula (4) wherein m is 3 to 20) with p-phenylene (paraphenylene), produced by Otsuka chemical Co., ltd.)

Almori B-325 (aluminum hydroxide: average particle diameter 27 μm, manufactured by Almori Ltd.)

B103 (aluminum hydroxide having an average particle diameter of 7 μm, manufactured by Nichijin Co., ltd.)

((E) ingredient: aminosilane)

Dynasilane1146 (diaminosilane-containing silane oligomer: low volatility, low viscosity (35 mPa. Multidot.s/20 ℃ C.), manufactured by Evonik corporation) (hydrolysis condensate of ethyltriethoxysilane and 3- [ N- (2-aminoethyl) amino ] propyltriethoxysilane, nitrogen atom content: 6% by mass)

(silanol condensing catalyst)

Neostan U-830 (dioctyltin dineodecanoate, manufactured by Nidonghua Co., ltd.)

(preparation of sample)

The component (A), the component (B), or the component (B'), the component (C), and the component (D) were mixed at a mixing ratio shown in Table 1 at 120 ℃. Thereafter, the component (E) and the silanol condensing catalyst were added to prepare samples according to examples 1 to 5 and comparative examples 1 to 5, respectively.

(evaluation of shape Retention)

Using the prepared samples according to example 1, test pieces (10 mm in length × 10mm in width × 1.5mm in thickness) cured at 23 ℃ and 50 RH for 1 week were prepared. The test piece was placed in an electric furnace (Yamato Scientific Co., ltd., model: FO300 type) and burned in air at 600 ℃ for 30 minutes. After the combustion, the inside of the electric furnace was kept at 23 ℃ and left for 12 hours. Thereafter, the state of the test piece was visually confirmed at 23 ℃ 50% RH. The shape retention was judged by the following criteria. In the same manner, examples 2 to 5 and comparative examples 1 to 5 were also evaluated.

O: expanded in a state of maintaining the shape of the test piece before combustion

Δ: the shape of the test piece before burning was maintained but a part of the test piece collapsed and expanded

X: expand without maintaining the shape of the test piece before burning

(evaluation of flame retardancy: UL94V test)

Using the prepared sample according to example 1, a test piece (127 mm in length, 12.7mm in width, 1.5mm in thickness) was prepared which was cured at 23 ℃ for 50% RH for 1 week. The upper end of the test piece was fixed to a jig and held vertically, and a 20mm flame was exposed to the flame for 10 seconds at the lower end. If the burning of the test piece was stopped within 30 seconds, the 20mm flame was further exposed to the flame for 10 seconds, and the burning time of the test piece after the 2 nd exposure to the flame was measured. In the same manner, the measurements were also performed for examples 2 to 5 and comparative examples 1 to 5.

(evaluation of storage stability period)

The initial viscosity was measured using the sample according to example 1, and then the sample was left in a closed container at 120 ℃ for 5 hours to measure the viscosity again (hereinafter referred to as storage stability period viscosity). The storage stability period was evaluated according to the following criteria. In the same manner, examples 2 to 5 and comparative examples 1 to 5 were also evaluated.

O: thickening ratio (viscosity at storage stability period ÷ initial viscosity) is less than 2.0 times

X: a thickening ratio (viscosity in storage stability period ÷ initial viscosity) of 2.0 times or more

Referring to table 1, it is seen that the one-pack room temperature moisture curable reactive hot melt compositions of examples 1 to 5 are excellent in flame retardancy and storage stability. In addition, with respect to shape retention, a small amount of collapse was observed in example 4, but any of the one-pack room temperature moisture-curable hot melt compositions described in the other examples showed excellent shape retention. On the other hand, comparative examples 1 to 4 had no shape-retaining property, and comparative example 5 exhibited shape-retaining property, but the storage stability period was inferior.

The embodiments and examples of the present invention have been described above, but the embodiments and examples described above do not limit the invention according to the claims. The following two points should be noted: all combinations of features described in the embodiments and examples are not limited to those necessary for solving the problems of the present invention, and various modifications may be made without departing from the technical spirit of the present invention.

Claims (8)

1. A method for forming a fire-resistant structure by using a one-pack room-temperature moisture-curable reactive hot-melt composition having fire resistance,

the one-pack room-temperature moisture-curable reactive hot melt composition retains its shape at a temperature of less than 80 ℃ after moisture curing,

the temperature of the one-pack room-temperature moisture-curable reactive hot melt composition after moisture curing when used under hot melt application conditions is 80 ℃ to 150 ℃,

the one-pack room-temperature moisture-curable reactive hot-melt composition after the moisture curing is subjected to a high temperature of 180 ℃ or higher to cause a thermosetting reaction, a heat-insulating layer-forming reaction, and a flame-retardant reaction of the one-pack room-temperature moisture-curable reactive hot-melt composition, thereby forming the refractory structure,

wherein the one-pack room-temperature moisture-curable reactive hot-melt composition comprises:

(A) An organic polymer having a moisture-curable group and being solid at ordinary temperature,

(B) An oxazine ring-containing resin as a high-temperature thermosetting flame-retardant resin having a thermosetting temperature of 180 ℃ or higher,

(C) Unexpanded microspheres or aluminum phosphite as a thermal expansion agent having a thermal expansion temperature of 180 ℃ or higher, and

(D) A flame retardant having a flame-retardant reaction temperature of 180 ℃ or higher.

2. The forming method according to claim 1,

the fire-resistant structure is formed by using a non-combustible or fire-retardant member and the one-pack room-temperature moisture-curable reactive hot melt composition having fire resistance.

3. The forming method according to claim 1,

the glass transition temperature of the organic polymer (A) having a moisture-curable group and being solid at normal temperature is-20 ℃ or higher and 50 ℃ or lower.

4. A one-pack room temperature moisture curable reactive hot melt composition having fire resistance, comprising:

(A) An organic polymer having a moisture-curable group and being solid at ordinary temperature,

(B) An oxazine ring-containing resin as a high-temperature thermosetting flame-retardant resin having a thermosetting temperature of 180 ℃ or higher,

(C) Unexpanded microspheres or aluminum phosphite as a thermal expansion agent having a thermal expansion temperature of 180 ℃ or higher, and

(D) A flame retardant having a flame-retardant reaction temperature of 180 ℃ or higher.

5. The one-pack room temperature moisture curable reactive hot melt composition with fire resistance according to claim 4, wherein,

the organic polymer (A) having a moisture-curable group and being solid at ordinary temperature is a (meth) acrylate polymer having a crosslinkable silicon group.

6. The one-pack room-temperature moisture-curable reactive hot melt composition with fire resistance according to claim 4, wherein,

the organic polymer (A) having a moisture-curable group and being solid at ordinary temperature is a (meth) acrylate polymer having a crosslinkable silicon group and having a glass transition temperature of-20 ℃ or higher and 50 ℃ or lower.

7. The one-pack room temperature moisture-curable reactive hot melt composition with fire resistance according to any one of claims 4 to 6, further comprising (E) an aminosilane.

8. An article having a cured product of the one-pack room-temperature moisture-curable reactive hot melt composition having fire resistance according to any one of claims 4 to 7.

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