JP2015074665A - Moisture-curable cipg composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a moisture-curable CIPG(Cured-In-Plastic Gasket) composition which is excellent in compression set, film hardness, and a waterproof property.SOLUTION: There is provided the moisture-curable CIPG composition containing : a polyoxyalkylene-based polymer having a crosslinkable silicon group at a terminal, the silicon group having a general formula represented by -SiX(X represents a hydroxyl group or a hydrolyzable group; and three X's may be the same or different); a (meth)acrylic acid-based plasticizer in an amount of 150 pts.mass or more and 400 pts.mass or less relative to 100 pts.mass of all polymer having arbitrary crosslinkable silicon groups; and an inorganic filler. It is preferred that the composition further contains a (meth)acrylic acid ester-based polymer having arbitrary crosslinkable silicon groups since the cured product of the composition containing such groups is excellent in both film hardness and compression set. Further, the it is preferred that the inorganic filler contains calcium carbonate since the cured product of the composition containing such an inorganic filler is excellent in film hardness.

Description

  The present invention relates to a moisture curable CIPG composition.

  In order to prevent internal fluid from leaking from a joint surface of a pipe or a device, it is known to sandwich a gasket between the joint surfaces. Among them, liquid gaskets are widely used in that they can be suitably used even when the joint surface is rough, there is no need to excessively tighten tubes and equipment, and deterioration due to aging, vibration, etc. can be suppressed. .

  As liquid gaskets, CIPG (Cured-In-Place Gasket) and FIPG (Formed-In-Place Gasket) are known. CIPG is a system in which an uncured liquid gasket composition is applied to the joint surface of one member, the composition is cured, and then the surface is joined to the other member. According to CIPG, since the liquid gasket composition is applied to only one member, the workability is excellent in that the members can be removed and reassembled. FIPG is a method in which an uncured liquid gasket composition is applied to the joint surfaces of both members, and the liquid gasket composition is cured after both members are joined at the joint surfaces while the liquid gasket composition is uncured. It is. According to FIPG, since no external force is applied to the cured product of the gasket composition, there is little creep phenomenon or sag of the gasket due to stress, and excellent long-term reliability. CIPG or FIPG is appropriately selected according to the application.

  By the way, when providing a CIPG composition, after hardening a composition, in order to carry out surface joining with the other member, it is calculated | required to improve the performance regarding a compression set. As those having excellent compression set, (A) a specific organopolysiloxane, (B) a specific organohydrogenpolysiloxane, (C) a platinum group metal catalyst, (D) a curing controller, (E ) Thermosetting CIPG compositions containing inorganic acid acceptors have been proposed. This composition is suitable for sealing joint surfaces of electronic parts such as transistors, ICs, CPUs, memories, sensors, and batteries, electric parts such as in-vehicle ECUs and sensors, and mobile devices.

JP 2007-161999 A

  However, the CIPG composition described in Patent Document 1 is a thermosetting type, and requires a heating device for curing the CIPG composition in a structure production line. There is a need to provide CIPG that is excellent in compression set, film hardness and waterproofness in a moisture-curing type in that a special apparatus for curing the CIPG composition is not required and versatility of the adherend is increased. It has been.

  This invention is made | formed in view of the said situation, The place made into the objective is providing the moisture curable CIPG composition excellent in compression set, film hardness, and waterproofness.

  The present inventor has conducted extensive research to solve the above-mentioned problems. As a result, the CIPG composition has a polyoxyalkylene polymer having a specific crosslinkable silicon group at its end and a predetermined amount of (meth) acrylic. It has been found that the above problems can be solved by containing an acid ester plasticizer and an inorganic filler, and the present invention has been completed. Specifically, the present invention provides the following.

(1) The present invention relates to a crosslinkable silicon represented by the general formula —SiX ₃ (wherein X represents a hydroxyl group or a hydrolyzable group, and three Xs may be the same or different). A polyoxyalkylene polymer having a terminal group and 150 to 400 parts by weight of a (meth) acrylate plasticizer with respect to 100 parts by weight of all polymers having any crosslinkable silicon group; And a moisture curable CIPG composition containing an inorganic filler.

  (2) Moreover, this invention is a moisture curable CIPG composition as described in (1) which further contains the (meth) acrylic acid ester-type polymer which has arbitrary crosslinkable silicon groups.

  (3) Moreover, this invention is the moisture curable CIPG composition as described in (1) or (2) in which the said inorganic filler contains a calcium carbonate.

  ADVANTAGE OF THE INVENTION According to this invention, the moisture curable CIPG composition excellent in compression set, film hardness, and waterproofness can be provided.

It is a schematic explanatory drawing of one housing | casing 10 used in order to evaluate the waterproofness of the moisture hardening CIPG composition which concerns on an Example and a comparative example. It is a schematic explanatory drawing of the other housing | casing 20 used in order to evaluate the waterproofness of the moisture hardening CIPG composition which concerns on an Example and a comparative example. After applying the moisture curable CIPG composition according to the example and the comparative example to the groove portion of the one casing 10 and curing the composition, the groove portion of the other casing 20 is assembled to the groove portion. It is an enlarged view of the fitting part when the structure 1 is formed by fitting.

  Hereinafter, specific embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and may be implemented with appropriate modifications within the scope of the object of the present invention. can do.

<Moisture curable CIPG composition>
The moisture curable CIPG composition of the present invention is represented by the general formula —SiX ₃ (wherein X represents a hydroxyl group or a hydrolyzable group, and three Xs may be the same or different). (Meth) acrylic acid ester of 150 parts by mass or more and 400 parts by mass or less with respect to 100 parts by mass of the polyoxyalkylene polymer having a crosslinkable silicon group at the terminal and any polymer having any crosslinkable silicon group Contains a plasticizer and an inorganic filler. Hereinafter, (A) resin component, (B) plasticizer, (C) inorganic filler, (D) curing catalyst, (E) solvent / diluent, and (F) other components will be described in this order.

[(A) Resin component]
[(A1) Polyoxyalkylene-based polymer having a terminal crosslinkable silicon group represented by the general formula —SiX ₃ ]
The moisture-curable CIPG composition of the present invention contains a polyoxyalkylene polymer having a crosslinkable silicon group at the terminal (A1) represented by the general formula —SiX ₃ as the resin component (A). Below, a resin component is also called (A) component and the said specific polyoxyalkylene type polymer is also called (A1) component.

(Crosslinkable silicon group)
The component (A1) is a polyoxyalkylene polymer having a crosslinkable silicon group represented by the general formula —SiX ₃ at the terminal. In this general formula, X represents a hydroxyl group or a hydrolyzable group, and the three Xs may be the same or different. Even if the CIPG composition contains a polyoxyalkylene polymer having a crosslinkable silicon group, if the crosslinkable silicon group is not represented by —SiX ₃ , the compression set of the cured product is not suitable. Since the airtightness of the structure may not be maintained, it is not preferable. In the present specification, the “crosslinkable silicon group” refers to a group that can be cross-linked by forming a siloxane bond by the action of moisture.

  It does not specifically limit as said hydrolysable group, What is necessary is just a conventionally well-known hydrolysable group. Examples thereof include a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, and an alkenyloxy group. Among these, a hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group, and an alkenyloxy group are preferable, and an alkoxy group, an amide group, and an aminooxy group are more preferable. An alkoxy group is particularly preferred from the viewpoint of mild hydrolysis and easy handling. Among the alkoxy groups, those having a smaller number of carbon atoms have higher reactivity, and the reactivity increases as the number of carbon atoms increases in the order of methoxy group> ethoxy group> propoxy group. Although it can be selected according to the purpose and use, a methoxy group or an ethoxy group is usually used.

Specific examples of the crosslinkable silicon group represented by the general formula —SiX ₃ include trialkoxysilyl groups (—Si (OR) ₃ ) such as a trimethoxysilyl group and a triethoxysilyl group. Here, R is an alkyl group such as a methyl group or an ethyl group.

Further, the crosslinkable silicon group represented by the general formula —SiX ₃ may be used alone or in combination of two or more. The crosslinkable silicon group may be present in the main chain or in the side chain as long as it is present at the molecular chain terminal. Crosslinkable silicon groups may be present in both the main chain and the side chain. If the crosslinkable silicon group is not present at the molecular chain terminal, it may affect the compression set of the cured product, which is not preferable.

The crosslinkable silicon group represented by the general formula —SiX ₃ may be present in at least one, preferably 1.1 to 5, in one molecule of the polyoxyalkylene polymer. When the number of crosslinkable silicon groups contained in the molecule is less than one, the curability is insufficient, and when the number is too large, the network structure becomes too dense, and good mechanical properties are not exhibited.

[Polyoxyalkylene polymer]
The polyoxyalkylene polymer is essentially a polymer having a repeating unit represented by the general formula -R ¹ -O-.

In —R ¹ —O—, R ¹ is a divalent alkylene group.

R ¹ is preferably a linear or branched alkylene group having 1 to 14 carbon atoms, more preferably 2 to 4 carbon atoms. Specific examples of the repeating unit represented by the general formula -R ¹ -O- include, for example,
Etc. The main chain skeleton of the polyoxyalkylene polymer may be composed of only one type of repeating unit, or may be composed of two or more types of repeating units. In particular, it is preferably made of a polymer mainly composed of oxypropylene.

  As a method for synthesizing a polyoxyalkylene polymer, for example, a polymerization method using an alkali catalyst such as KOH, for example, organic aluminum as disclosed in JP-A Nos. 61-197631, 61-215622, 61-215623 A polymerization method using an organoaluminum-porphyrin complex catalyst obtained by reacting a compound with porphyrin, for example, a polymerization method using a double metal cyanide complex catalyst described in JP-B-46-27250 and JP-B-59-15336 Although it is mentioned, it is not particularly limited. A polyoxyalkylene system having a narrow molecular weight distribution with a high molecular weight having a number average molecular weight of 6,000 or more and Mw / Mn of 1.6 or less according to a polymerization method using an organic aluminum-porphyrin complex catalyst or a polymerization method using a double metal cyanide complex catalyst A polymer can be obtained. In the present specification, the number average molecular weight is a value in terms of polystyrene when measured by gel permeation chromatography (GPC).

  The main chain skeleton of the polyoxyalkylene polymer may contain other components such as a urethane bond component. Examples of the urethane bond component include aromatic polyisocyanates such as toluene (tolylene) diisocyanate, diphenylmethane diisocyanate, and xylylene diisocyanate; aliphatic polyisocyanates such as isophorone diisocyanate and hexamethylene diisocyanate; and polyoxyalkylenes having a hydroxyl group. What can be obtained from this reaction can be mentioned.

  The introduction of a crosslinkable silicon group into a polyoxyalkylene polymer can be performed on a polyoxyalkylene polymer having a functional group such as an unsaturated group, a hydroxyl group, an epoxy group or an isocyanate group in the molecule. The reaction can be carried out by reacting a compound having a reactive functional group and a crosslinkable silicon group (hereinafter referred to as a polymer reaction method). As a specific example of the polymer reaction method, a hydrosilane or mercapto compound obtained by allowing a hydrosilane having a crosslinkable silicon group or a mercapto compound having a crosslinkable silicon group to act on an unsaturated group-containing polyoxyalkylene polymer to form a crosslinkable silicon group The method of obtaining the polyoxyalkylene type polymer which has can be mentioned. An unsaturated group-containing polyoxyalkylene-based polymer is obtained by reacting an organic polymer having a functional group such as a hydroxyl group with an organic compound having an active group and an unsaturated group that are reactive with the functional group. A polyoxyalkylene polymer containing can be obtained. Other specific examples of the polymer reaction method include a method of reacting a polyoxyalkylene polymer having a hydroxyl group at a terminal with a compound having an isocyanate group and a crosslinkable silicon group, or a polyoxyalkylene system having an isocyanate group at a terminal. Examples thereof include a method in which a polymer is reacted with a compound having an active hydrogen group such as a hydroxyl group or an amino group and a crosslinkable silicon group. When an isocyanate compound is used, a polyoxyalkylene polymer having a crosslinkable silicon group can be easily obtained.

  The component (A1) may be linear or branched. The molecular weight is preferably about 500 to 50,000 in terms of number average molecular weight, and more preferably 1,000 to 30,000. When the number average molecular weight is larger than 50,000, the viscosity of the composition becomes high, and the coating workability may be lowered. When the number average molecular weight is smaller than 500, the film hardness may be increased.

[(A2) (Meth) acrylic ester polymer having any crosslinkable silicon group]
Although not an essential component, the moisture curable CIPG composition of the present invention further comprises (A) a (meth) acrylic acid ester-based polymer having an arbitrary crosslinkable silicon group as the resin component (A). Is preferred. (A) When the component (A1) and the component (A2) are used in combination as the resin component, it is excellent in compression set of the cured product. Therefore, in the present invention, the component (A1) and the component (A2) are used in combination. Is particularly suitable.

(Crosslinkable silicon group)
The kind of the crosslinkable silicon group is not particularly limited and is arbitrary. That is, the crosslinkable silicon group may have a general formula represented by —SiX ₃ or may be another group. Examples of other crosslinkable silicon groups include groups represented by the following general formula (1).

In General Formula (1), R ² is an 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, an aralkyl group having 7 to 20 carbon atoms, or R ^2. ₃ represents a triorganosiloxy group represented by SiO— (R ² is the same as above), and when two or more R ² are present, they may be the same or different. X represents a hydroxyl group or a hydrolyzable group. When two or more X are present, they may be the same or different. a is an integer of 1 or 2.

Specific examples of the crosslinkable silicon group represented by the formula (1) include dialkoxysilyl groups (—SiR ² (OR) ₂ ) such as methyldimethoxysilyl group and methyldiethoxysilyl group. Here, R is an alkyl group such as a methyl group or an ethyl group.

  As in the case of the component (A1), at least one crosslinkable silicon group is present in one molecule of the (meth) acrylic acid ester polymer, preferably 1.1 to 5, and the (meth) acrylic acid ester polymer molecule. It may be present at the end of the chain, may be present inside, or may be present at both. In view of excellent compression set of the cured product, it is preferable that a crosslinkable silicon group is present at the end of the molecular chain. When the number of crosslinkable silicon groups in one molecule of the (meth) acrylic acid ester polymer is less than 1, it is not preferable because sufficient adhesiveness may not be obtained. When the number of crosslinkable silicon groups exceeds 5, it is not preferable in that the viscosity of the composition may be too high.

[(Meth) acrylic acid ester polymer]
The (meth) acrylic acid ester polymer is a polymer having a repeating unit essentially represented by the formula (2).

In the formula (2), R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents an alkyl group.

R ⁴ in formula (2) is an alkyl group, preferably an alkyl group having 1 to 30 carbon atoms. R ⁴ may be linear or branched. Or the substituted alkyl group which has a rogen atom, a phenyl group, etc. may be sufficient. Examples of R ⁴ include methyl group, ethyl group, propyl group, n-butyl group, t-butyl group, 2-ethylhexyl group, lauryl group, tridecyl group, cetyl group, stearyl group, and behenyl group. it can.

  The molecular chain of the (meth) acrylic acid alkyl ester polymer consists essentially of the monomer unit of the formula (2), and the term “essentially” as used herein refers to a formula ( It means that the total of the monomer units of 2) exceeds 50% by weight. The total of the monomer units of the formula (2) is preferably 70% by weight or more.

  Examples of monomer units other than formula (2) include monomer units derived from (meth) acrylic acid such as acrylic acid and methacrylic acid; acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide Monomer units derived from monomers containing amide groups such as: monomer units derived from monomers containing epoxy groups such as glycidyl acrylate and glycidyl methacrylate; diethylaminoethyl acrylate, diethylaminoethyl methacrylate, aminoethyl vinyl ether Monomer units derived from monomers containing amino groups such as acrylonitrile, styrene, α-methylstyrene, alkyl vinyl ether, vinyl chloride, vinyl acetate, vinyl propionate, ethylene, etc. Can be mentioned.

When the component (A1) and the component (A2) are used in combination as the resin component (A), the component (A2) has a crosslinkable silicon group in terms of high compatibility with the component (A1). A (meth) acrylate monomer unit having a molecular chain represented by the following formula (3) and a crosslinkable silicon group, and a molecular chain represented by the following formula (4) A copolymer composed of monomer units is preferred.

In Formula (3), R ³ is the same as above, and R ⁵ represents an alkyl group having 1 to ⁵ carbon atoms. In Formula (4), R ³ is the same as above, and R ⁶ represents an alkyl group having 6 or more carbon atoms.

As R < ⁵ > of said Formula (3), C1-C5, such as a methyl group, an ethyl group, a propyl group, n-butyl group, t-butyl group etc., Preferably it is 1-4, More preferably, it is 1-2. Of the alkyl group. Incidentally, R ⁵ may be a kind, or may be a mixture of two or more.

R ^{6 in the} above formula (4) is, for example, 2-ethylhexyl group, lauryl group, tridecyl group, cetyl group, stearyl group, behenyl group and the like having 6 or more carbon atoms, usually 7-30, preferably 8-20. Long chain alkyl groups can be mentioned. R ⁶ may be a single type or a mixture of two or more types. Further, the abundance ratio of the monomer unit of the formula (3) and the monomer unit of the formula (4) is preferably 95: 5 to 40:60, and more preferably 90:10 to 60:40 by weight.

  The component (A2) can usually be obtained by radical copolymerization of (meth) acrylic acid alkyl ester and (meth) acrylic acid alkyl ester having a crosslinkable silicon group. Further, when an initiator having a crosslinkable silicon group or a chain transfer agent having a crosslinkable silicon group is used, the crosslinkable silicon group can be introduced into the molecular chain terminal.

  (A) When the component (A1) and the component (A2) are used in combination as the resin component, the weight ratio of the component (A1) to the component (A2) is within the range of 95: 5 to 60:40. It is preferable that it is within a range of 90:10 to 70:30. When the amount of the component (A2) is too small, the compression set is inferior, and when the amount of the component (A2) is too large, the film hardness is inferior.

  JP 2001-040037 A, JP 2003-048923 A and JP 2003-048924 A have a crosslinkable silicon group (meth) obtained by using a mercaptan having a crosslinkable silicon group and a metallocene compound. Acrylic acid alkyl ester polymers are described. Moreover, the synthesis example of Unexamined-Japanese-Patent No. 2005-026881 describes the (meth) acrylic-acid alkylester type polymer which has a crosslinkable silicon group by high temperature continuous polymerization.

  As disclosed in JP-A-2000-086999, a (meth) acrylic acid alkyl ester-based polymer having a crosslinkable silicon group, in which a crosslinkable silicon group is introduced at a high ratio at the molecular chain terminal, Are known. Since such a polymer is produced by living radical polymerization, a crosslinkable silicon group can be introduced into the molecular chain terminal at a high rate. In the present invention, a (meth) acrylic acid alkyl ester polymer as described above can be used.

  Specific examples of a (meth) acrylic acid ester-based polymer having a crosslinkable silicon group and a mixture of this polymer and an oxyalkylene polymer having a crosslinkable silicon group are disclosed in JP-A Nos. 59-122541 and 63-112642. And in each publication such as JP-A-6-172631. JP-A-59-78223, JP-A-59-168014, JP-A-60-228516, JP-A-60-228517, etc. disclose oxyalkylene polymers having a crosslinkable silicon group. (Meth) acrylic acid ester-based monomer is polymerized in the presence of a mixture of an oxyalkylene polymer having a crosslinkable silicon group and a (meth) acrylic acid alkyl ester polymer having a crosslinkable silicon group. The method of obtaining is described.

[(A3) Other resin components]
Component (A) is a description relating to the resin component, but (A3) other resin component, that is, a crosslinkable silicon group that is widely known in the range that does not affect the compression set and film hardness. Even a polyoxyalkylene polymer or a (meth) acrylic acid ester polymer may be used.

[(B) (Meth) acrylic ester plasticizer]
The moisture-curable CIPG composition of the present invention contains (B) (meth) acrylic acid ester plasticizer. In the following, the (B) (meth) acrylic acid ester plasticizer is also referred to as a component (B).

  The plasticizer is added for the purpose of adjusting the hardness after curing. In the present invention, when the plasticizer is not a (meth) acrylic acid ester, even if the moisture curable CIPG composition contains a plasticizer, the compression set of the cured product does not fall within the preferred range. It is not preferable.

  Examples of (meth) acrylate plasticizers include UP-1000 (manufactured by Toagosei Co., Ltd.), UP-1080 (manufactured by Toagosei Co., Ltd.), UP-1110 (manufactured by Toagosei Co., Ltd.) and UP. Hydroxyl group-free acrylic plasticizers such as -1061 (manufactured by Toagosei Co., Ltd.); hydroxyl groups such as UP-2000 (manufactured by Toagosei Co., Ltd.), UHE-2012 (manufactured by Toagosei Co., Ltd.) Acrylic plasticizers; carboxyl group-containing acrylic polymers such as UC-3510 (manufactured by Toagosei Co., Ltd.); epoxy group-containing acrylic polymers such as UG-4000 (manufactured by Toagosei Co., Ltd.); US- And (meth) acrylic polymers containing less than 0.5 silyl groups, such as 6110 (manufactured by Toagosei Co., Ltd.), US-6120 (manufactured by Toagosei Co., Ltd.), and the like. Of these, hydroxyl group-free (meth) acrylic plasticizers are preferred.

  (B) Content of a component is 150 to 400 mass parts with respect to 100 mass parts of all the polymers which have arbitrary crosslinkable silicon groups, and it is preferable that it is 200 to 300 mass parts. When there is too little content of (B) component, it may not be suitable at the point of the film hardness and compression set of hardened | cured material. When the content of the component (B) is too large, the compression set of the cured product is not suitable, and as a result, the airtightness of the structure may not be maintained.

  Component (B) is a description relating to a plasticizer, but it contains other plasticizers, that is, plasticizers that are widely known as long as they do not affect compression set and film hardness. There is no problem. Examples of other plasticizers include: phthalates such as diisoundecyl phthalate; aliphatic dibasic esters such as dioctyl adipate; glycol esters such as diethylene glycol dibenzoate; butyl oleate and the like Aliphatic esters; Phosphate esters such as tricresyl phosphate; Epoxy plasticizers such as epoxidized soybean oil; Polyester plasticizers; Polyethers such as polypropylene glycol derivatives; Tetraethylene glycol diethyl ether Polyoxyethylene alkyl ethers; Polystyrene oligomers such as poly-α-methylstyrene; Hydrocarbon oligomers such as polybutadiene; Chlorinated paraffins; Oxyalkylene resins containing less than 0.5 silyl groups Can be mentioned.

[(C) inorganic filler]
The moisture-curable CIPG composition of the present invention contains (C) an inorganic filler. Hereinafter, the (C) inorganic filler is also referred to as the (C) component.

  The type of the inorganic filler is not particularly limited, and carbon dioxide such as fumed silica, precipitated silica, anhydrous silicic acid, hydrous silicic acid and carbon black, fine calcium carbonate, heavy calcium carbonate, or surface treated products thereof. Calcium, alumina, aluminum hydroxide, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, kaolin, titanium oxide, bentonite, organic bentonite, ferric oxide, zinc oxide, activated zinc white, glass balloon, shirasu balloon and inorganic Examples thereof include fibers.

  One type of inorganic filler may be used, or a mixture of two or more types may be used. Especially, it is preferable that an inorganic filler is a calcium carbonate at the point which is excellent in the compression set of hardened | cured material. The calcium carbonate may be colloidal calcium carbonate having an average particle diameter of 1 micron or less, or may be heavy calcium carbonate having an average particle diameter of more than 1 micron. The inorganic filler may be a mixture of colloidal calcium carbonate and heavy calcium carbonate.

  Calcium carbonate may or may not be surface treated. As surface-treated calcium carbonate, calcium carbonate surface-treated with a higher fatty acid or a derivative such as a metal salt or ester thereof is well known.

  Although content of (C) component is not specifically limited, It is preferable that it is 1 to 300 mass parts with respect to 100 mass parts of all the polymers which have arbitrary crosslinkable silicon groups, and 50 mass parts The amount is more preferably 300 parts by mass or less, and further preferably 100 parts by mass or more and 200 parts by mass or less. (C) When there is too little content of an inorganic filler, since a compression set and waterproofness may fall, it is unpreferable. (C) When there is too much content of an inorganic filler, since the viscosity of a composition becomes high and workability | operativity may fall, it is unpreferable.

[(D) Curing catalyst]
Moreover, although it is not an essential component, the moisture-curable CIPG composition of the present invention may contain (D) a curing catalyst. Hereinafter, the (D) curing catalyst is also referred to as the (D) component.

  (D) The kind of curing catalyst is not specifically limited, For example, an organometallic compound, amines, etc. are mentioned, It is preferable to use a silanol condensation catalyst especially. Examples of the silanol condensation catalyst include titanic acid esters such as tetrabutyl titanate, tetrapropyl titanate, tetraisopropyl titanate, titanium tetraacetylacetonate; dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, dibutyltin diacetylacetate. Nert, dibutyltin oxide, dioctyltin dilaurate, dioctyltin maleate, dioctyltin diacetate, dioctyltin dineodecanate (dioctyltin diversate), dioctyltin oxide, reaction product of dibutyltin oxide and phthalate, dibutyl complex salt and orthoethyl silicate Reaction products, tetravalent tin compounds such as reaction products of dioctyltin oxide and normal ethyl silicate, tin dioctylate, tin dinaphthenate, distearin Organic tin compounds such as divalent tin compounds such as tin and tin dineodecanoate (tinversic acid tin); organoaluminum compounds such as aluminum trisacetylacetonate, aluminum trisethylacetoacetate, diisopropoxyaluminum ethylacetoacetate; bismuth -Reaction products of bismuth salts such as tris (2-ethylhexoate), bismuth-tris (neodecanoate) and organic carboxylic acids or organic amines; chelating compounds such as zirconium tetraacetylacetonate and titanium tetraacetylacetonate Organic lead compounds such as lead octylate; organic iron compounds such as iron naphthenate; organic vanadium compounds; butylamine, octylamine, laurylamine, dibutylamine, monoethanolamine, diethanolamine, trie Nolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris (dimethylaminomethyl) phenol, morpholine, N- Amine compounds such as methylmorpholine, 2-ethyl-4-methylimidazole, 1,8-diazabicyclo (5,4,0) undecene-7 (DBU) or salts thereof with carboxylic acids, etc .; excess polyamines and many Examples include low molecular weight polyamide resins obtained from basic acids; reaction products of excess polyamines and epoxy compounds, and the like.

  These curing catalysts may be used alone or in combination of two or more. Of these curing catalysts, organometallic compounds or a combined system of organometallic compounds and an amine compound are preferred from the viewpoint of curability. Furthermore, dibutyltin maleate, a reaction product of dibutyltin oxide and phthalate, a reaction product of dioctyltin oxide and normal ethyl silicate, dibutyltin diacetylacetonate, and dioctyltin dineodecanate are preferred from the viewpoint of high curing speed. Moreover, a dioctyl tin compound is preferable from the viewpoint of environmental problems. The content of the curing catalyst is preferably 0.1 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of all polymers having an arbitrary crosslinkable silicon group.

[(E) solvent or diluent]
Moreover, although it is not an essential component, the moisture-curable CIPG composition of the present invention may contain (E) a solvent or a diluent. Hereinafter, (E) the solvent / diluent is also referred to as (E) component.

  The component (E) is used for improving workability and reducing the viscosity.

  Examples of the solvent include aromatic hydrocarbon solvents such as toluene and xylene; ester solvents such as ethyl acetate, butyl acetate, amyl acetate, and cellosolve; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone. Examples of the diluent include normal paraffin and isoparaffin.

  (E) Although content of a component is not specifically limited, It is preferable that it is 1 mass part or more and 100 mass parts or less with respect to 100 mass parts of all the polymers which have a crosslinkable silicon group, and 5 mass parts or more. More preferably, it is 50 parts by mass or less.

[(F) Other ingredients]
The moisture-curable CIPG composition of the present invention may contain commonly used additives as long as the object of the present invention is not impaired. Additives include tackifiers, tackifiers, anti-sagging agents (hydrogenated castor oil, organic bentonite, calcium stearate, etc.), colorants, antioxidants, ultraviolet absorbers, light stabilizers, and the like. . Also included are physical property modifiers, storage stability improvers (dehydrating agents), lubricants, foaming agents, and the like.

(Adhesive agent)
Examples of the adhesion-imparting agent include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- Amino group-containing silanes such as (β-aminoethyl) -γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, 1,3-diaminoisopropyltrimethoxysilane; Epoxy group-containing silanes such as glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane Γ-mercaptopropyltrimethoxysilane, Mercapto group-containing silanes such as γ-mercaptopropylmethyldimethoxysilane; vinyl-type unsaturated groups such as vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, and γ-acryloyloxypropylmethyldimethoxysilane Silanes; Chlorine atom-containing silanes such as γ-chloropropyltrimethoxysilane; Isocyanate-containing silanes such as γ-isocyanatopropyltriethoxysilane and γ-isocyanatopropylmethyldimethoxysilane; methyldimethoxysilane, trimethoxysilane, methyldi Specific examples include hydrosilanes such as ethoxysilane, but are not limited thereto.

  If the adhesiveness-imparting agent is added too much, the film hardness of the cured product is increased, and if it is too small, the adhesiveness is lowered. It is preferable to add 1 part by mass or more and 15 parts by mass or less, and more preferably 0.5 part by mass or more and 10 parts by mass or less.

[Tackifier]
The tackifier is preferable for improving the wettability to the adherend and increasing the peel strength. Examples include, but are not limited to, petroleum resin-based, rosin / rosin ester-based, acrylic resin-based, terpene resin, hydrogenated terpene resin and its phenolic resin copolymer, phenol / phenol novolac resin-based tackifier resin, etc. It is not something. The tackifier is preferably added in an amount of 1 part by mass or more and 100 parts by mass or less, more preferably 5 parts by mass or more and 50 parts by mass or less, based on 100 parts by mass of all polymers having a crosslinkable silicon group.

[Other features]
The moisture curable CIPG composition of the present invention may be a one-component composition comprising all components as a mixture, or a two-component composition comprising a resin component having a crosslinkable silicon group and a curing catalyst component as separate components. It is good also as a thing. In general, the two-part composition is superior in various properties as compared to the one-part type, but the moisture-curable CIPG composition is a one-part type in that the operation of mixing the resin component and the curing catalyst component can be omitted. Preferably there is.

[Production method]
The method for producing the moisture curable CIPG composition of the present invention is not particularly limited. For example, the above-described components are blended and kneaded using a mixer, a roll, a kneader, or the like at room temperature or under heating. The usual methods, such as using a small amount of a solvent to dissolve and mixing the components, can be mentioned.

[Usage]
The composition of the present invention is suitably used as a CIPG composition because it is cured at normal temperature (0 ° C. to 40 ° C.) by atmospheric moisture. Among them, electronic parts exemplified by transistors, ICs, CPUs, memories, sensors, batteries, electrical parts such as in-vehicle ECUs, sensors, structural parts exemplified by mobile devices, etc. It is useful for sealing window frames and sashes, curtain walls, various exterior panels, and the like. In addition, although the CIPG composition of this invention is hardened | cured at normal temperature (0 degreeC-40 degreeC) with the humidity in air | atmosphere, you may accelerate | stimulate hardening suitably by heating as needed.

  First, an uncured CIPG composition is applied to the joint surface of one member, and after the composition is cured, the surface is joined to the other member. Thereby, a joint surface can be sealed suitably.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention does not receive a restriction | limiting at all in these description.

<Synthesis of resin components>

[Synthesis Example 1]
A methanol solution of sodium methoxide (NaOMe) was added to propylene glycol to distill off the methanol, and allyl chloride was further added to convert the terminal hydroxyl group to an allyl group. Unreacted allyl chloride was removed by devolatilization under reduced pressure, and the resulting metal salt was extracted and removed with water to obtain polyoxypropylene having an allyl group at the terminal. An isopropanol solution of a platinum vinylsiloxane complex is added to the resulting allyl group-terminated polyoxypropylene and reacted with trimethoxysilane to have a number average molecular weight of about 25,000 and 1.5 terminal trimethoxysilyl groups per molecule. A polyoxypropylene-based polymer having was obtained.

[Synthesis Example 2]
In a flask, 40 parts by weight of ethyl acetate as a solvent, 59 parts by weight of methyl methacrylate, 25 parts by weight of 2-ethylhexyl methacrylate, 22 parts by weight of γ-methacryloxypropyltrimethoxysilane, and 0.1 part by weight of ruthenocene dichloride as a metal catalyst were added. The mixture was heated to 80 ° C. while introducing charged nitrogen gas. Then, 8 parts by weight of 3-mercaptopropyltrimethoxysilane was added to the flask and reacted at 80 ° C. for 6 hours. After cooling to room temperature, 20 parts by weight of a benzoquinone solution (95% THF solution) was added to terminate the polymerization. The solvent and unreacted material were distilled off, and the (meth) acrylic group having a trimethoxysilyl group having a polystyrene-equivalent weight average molecular weight of about 6000, Mw / Mn of 1.6, and Tg of 61.2 ° C. An acid ester polymer was obtained.

[Synthesis Example 3]
In a flask, 40 parts by weight of ethyl acetate as a solvent, 59 parts by weight of methyl methacrylate, 25 parts by weight of 2-ethylhexyl methacrylate, 22 parts by weight of γ-methacryloxypropylmethyldimethoxysilane, and 0.1 part by weight of ruthenocene dichloride as a metal catalyst were added. The mixture was heated to 80 ° C. while introducing charged nitrogen gas. Next, 8 parts by weight of 3-mercaptopropylmethyldimethoxysilane was added to the flask and reacted at 80 ° C. for 6 hours. After cooling to room temperature, 20 parts by weight of a benzoquinone solution (95% THF solution) was added to terminate the polymerization. The solvent and unreacted material were distilled off, and the (meth) acrylic acid having a methyldimethoxysilyl group having a polystyrene-equivalent weight average molecular weight of about 6000, Mw / Mn of 1.6, and Tg of 61.2 ° C. An acid ester polymer was obtained.

[Synthesis Example 4]
A solution prepared by dissolving 2,2′-azobis (2-methylbutyronitrile) as a polymerization initiator in a toluene solution of the monomer mixture shown in Table 2 below heated to 105 ° C. was dropped over 5 hours, and then “Post-polymerization” was performed for 1 hour, and the solvent was distilled off under reduced pressure to obtain a vinyl copolymer.

[Synthesis Example 5]
A methanol solution of sodium methoxide (NaOMe) was added to propylene glycol to distill off the methanol, and allyl chloride was further added to convert the terminal hydroxyl group to an allyl group. Unreacted allyl chloride was removed by devolatilization under reduced pressure, and the resulting metal salt was extracted and removed with water to obtain polyoxypropylene having an allyl group at the terminal. To the resulting allyl group-terminated polyoxypropylene, an isopropanol solution of a platinum vinylsiloxane complex is added and reacted with methyldimethoxysilane to have a number average molecular weight of about 25,000 and 1.8 terminal methyldimethoxysilyl groups per molecule. A polyoxypropylene-based polymer having was obtained.

<Preparation of moisture curable CIPG composition>

In Table 3, various materials are as follows.
(A) Resin component (A1) Polyoxyalkylene polymer having a terminal crosslinkable silicon group represented by the general formula —SiX ₃ Synthesis Example 1 synthesized in the above <Synthesis of Resin Component>
(A2) (Meth) acrylic acid ester polymer having any crosslinkable silicon group Synthesis Examples 2 to 4 synthesized in the above <Synthesis of Resin Component>
(A3) Other resin components Synthesis Example 5 synthesized in the above <Synthesis of resin components>
(B) (Meth) acrylic ester plasticizer Non-functional acrylic plasticizer (Product name: ARUFUON UP-1110, manufactured by Toagosei Co., Ltd.)
(B ′) Other plasticizers Polypropylene glycol (trade name: Actcol D-3000, number average molecular weight: 3000, manufactured by Mitsui Chemicals, Inc.)
Diisononyl phthalate (C) inorganic filler Fatty acid-treated calcium carbonate (Product name: Calfine 200, manufactured by Maruo Calcium Co., Ltd.)
Heavy calcium carbonate (Product name: Whiten SB, manufactured by Shiroishi Calcium)
Hydrophobic fumed silica (Product name: AEROSIL RY200S, manufactured by Nippon Aerosil Co., Ltd.)
Aluminum hydroxide (Product name: C-303, manufactured by Sumitomo Chemical Co., Ltd.)
(D) Curing catalyst Curing catalyst 1 (Product name: Neostan S-1, reaction product of dioctyltin oxide and normal ethyl silicate, manufactured by Nitto Kasei Co., Ltd.)
(E) Solvent / Diluent Paraffinic Diluent (Product name: Cactus normal paraffin N-11, manufactured by JX Nippon Oil & Energy Corporation)
(F) Other components Adhesion imparting agent (Product name: KBM603, N-β (aminoethyl) -γ-aminopropyltriethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.)
Antioxidant (Product name: Irganox 245, hindered phenol antioxidant, manufactured by BASF)
Dehydrating agent (Product name: ethyl silicate 28, tetraethoxysilane, manufactured by Colcoat)
Sagging inhibitor (Product name: Disparon 308, hydrogenated castor oil, manufactured by Enomoto Kasei Co., Ltd.)

  The materials shown in Table 3 were charged into a mixer at a mass ratio shown in Table 3, and mixed by stirring to obtain moisture curable CIPG compositions according to Examples and Comparative Examples.

<Evaluation>
About the moisture hardening CIPG composition which concerns on an Example and a comparative example, film hardness, compression set, and waterproofness were evaluated.

[Film hardness]
In order to evaluate the film hardness, the Shore A hardness of the moisture curable CIPG compositions according to Examples and Comparative Examples was measured according to JIS K6253 using a type A durometer (manufactured by Ueshima Seisakusho). Under conditions of 23 ° C. and 50% RH, the moisture curable CIPG compositions according to Examples and Comparative Examples were blended in a polyethylene cup having a diameter of 30 mm and a depth of 8 mm, respectively, and then the surface was putty knife And then cured under conditions of 23 ° C. and 50% RH for 1 week. Then, hardened | cured material was taken out from the cup and it was set as the test piece. A case where the hardness was 20 or less was indicated as “◯”, and a case where the hardness exceeded 20 was indicated as “x”. The results are shown in Table 4.

[Compression set]
The film hardness was measured according to JIS K6262. First, cylindrical shaped bodies of moisture-curable CIPG compositions according to Examples and Comparative Examples having a diameter of 30.0 mm and a thickness of 12.0 mm were prepared, and 9.0 mm using a spacer according to JIS K6262. Until it was compressed and left under conditions of 100 ° C. for 22 hours. After the compression was finished, it was allowed to stand at 23 ° C. for 30 minutes, and then the thickness H of the molded body was measured, and (12.0−H) / (12.0−9.0) × 100 was determined as compression set. (Unit:%). A case where the compression set was 50% or less was indicated as “◯”, a case where the compression set exceeded 50%, a case where it was 60% or less was indicated as “Δ”, and a case where the compression set exceeded 60% was indicated as “X”. The results are shown in Table 4.

[Waterproof]
Using a dispenser robot equipped with a needle having an inner diameter of 0.33 mm as a discharge needle, the moisture curable CIPG compositions according to Examples and Comparative Examples are provided in the groove of one casing 10 (made of polycarbonate resin) shown in FIG. The composition was applied and cured. Then, the groove part of the other housing | casing 20 (product made from polycarbonate resin) shown in FIG. 2 was assembled | attached and fitted to the said groove part as shown in FIG. And the waterproofing test was implemented after leaving the structure 1 after fitting for 72 hours at 23 degreeC and 50% RH.

  For the waterproof test, a simple waterproof tester S-480S (manufactured by Seiko) was immersed in water under a predetermined pressure at 23 ° C. for 5 minutes, and then visually checked whether water had entered the packing. Judged. The case where water intrusion was not recognized was indicated as “◯”, and the case where it was recognized as “×”. The results are shown in Table 4.

150 parts by mass or more and 400 parts by mass or less with respect to 100 parts by mass of the polyoxyalkylene polymer having a crosslinkable silicon group represented by the general formula —SiX ₃ and any polymer having a crosslinkable silicon group. When it is a moisture curable CIPG composition containing a (meth) acrylic ester plasticizer and an inorganic filler, it is confirmed that the cured product is excellent in all of film hardness, compression set and waterproofness. (Examples 1-5). By comparing Examples 1, 2 and 5 with Example 3, the resin component is a polyoxy having a crosslinkable silicon group represented by the general formula —SiX ₃ in that the cured product is excellent in compression set. It can be said that the mixture is preferably a mixture of an alkylene polymer and a (meth) acrylic acid ester polymer having an arbitrary crosslinkable silicon group (Examples 1, 2 and 5). The crosslinkable silicon group of the (meth) acrylic acid ester polymer is not limited to the crosslinkable silicon group represented by —SiX ₃ , and any crosslinkable silicon group is sufficient (Examples 1 and 5). ). Moreover, by comparing Examples 1 and 2, it can be said that it is preferable that the CIPG composition further contains a solvent or a diluent which is the component (E) in that the cured product is excellent in compression set. 1). Further, by comparing Examples 1 and 4, it can be said that the filler is preferably calcium carbonate in terms of excellent compression set of the cured product (Example 1).

On the other hand, when the resin component does not contain a polyoxyalkylene polymer having a crosslinkable silicon group represented by the general formula —SiX ₃ , either or both of the film hardness and the compression set are not suitable. Since either or both of the softness of the CIPG cured product and the airtightness of the structure may not be suitable, it is not preferable (Comparative Examples 1 and 2). Moreover, when there is too little content of (B) (meth) acrylic-ester type plasticizer, both film hardness and compression set are not suitable, As a result, the softness of CIPG hardened | cured material and the airtightness of a structure Since both are not suitable, it is not preferable (Comparative Example 3). And when there is too much content of (B) (meth) acrylic acid ester plasticizer, since compression set is not suitable and, as a result, the airtightness of the structure may not be maintained, it is not preferable. (Comparative Example 4). Further, even if the CIPG composition contains a plasticizer, if the plasticizer is not a (meth) acrylic acid ester, the compression set is not suitable, and as a result, the airtightness of the structure can be maintained. Since it may be impossible, it is not preferable (Comparative Examples 5 to 7).

DESCRIPTION OF SYMBOLS 1 Structure 10 1st housing | casing 20 2nd housing | casing 30 Hardened | cured material of moisture curable CIPG composition

[Compression set]
The compression set was measured according to JIS K6262. First, cylindrical shaped bodies of moisture-curable CIPG compositions according to Examples and Comparative Examples having a diameter of 30.0 mm and a thickness of 12.0 mm were prepared, and 9.0 mm using a spacer according to JIS K6262. Until it was compressed and left under conditions of 100 ° C. for 22 hours. After the compression was finished, it was allowed to stand at 23 ° C. for 30 minutes, and then the thickness H of the molded body was measured, and (12.0−H) / (12.0−9.0) × 100 was determined as compression set. (Unit:%). A case where the compression set was 50% or less was indicated as “◯”, a case where the compression set exceeded 50%, a case where it was 60% or less was indicated as “Δ”, and a case where the compression set exceeded 60% was indicated as “X”. The results are shown in Table 4.

Claims (3)

A polyoxy having a terminal crosslinkable silicon group represented by the general formula —SiX ₃ (wherein X represents a hydroxyl group or a hydrolyzable group, and three Xs may be the same or different). An alkylene polymer;
150 parts by weight or more and 400 parts by weight or less (meth) acrylic ester plasticizer with respect to 100 parts by weight of all polymers having an arbitrary crosslinkable silicon group;
A moisture curable CIPG composition containing an inorganic filler.   The moisture-curable CIPG composition according to claim 1, further comprising a (meth) acrylic acid ester-based polymer having an arbitrary crosslinkable silicon group.   The moisture-curable CIPG composition according to claim 1 or 2, wherein the inorganic filler contains calcium carbonate.