JP5735854B2 - Fusing agent - Google Patents

Description

  The present invention relates to a fusing agent that is made of polysilane and is useful for joining resins and the like, an injector filled with the fusing agent, and a joining method using the fusing agent.

  Fusion is widely used as one of bonding methods, and is usually performed by interposing or adhering a fusion agent to a portion requiring fusion, that is, a fusion interface. In such a bonding method, it is important to remove as much as possible deposits (for example, water, oxide film, sand, dust, dust, etc.) at the fusion interface because the fusion strength of the fusion agent is reduced. Examples of methods for removing the interface deposit before fusing include scraping the fusing interface and wiping with an organic solvent. However, when the fusion is performed under natural conditions such as outdoors, fine sand particles and the like adhere to the fusion interface even if the removal method is applied, and the fusion strength is lowered.

  In such fusion, it has been proposed to use a silicon-containing polymer such as polysilane as a fusion agent. In WO98 / 46928 (Patent Document 1), when a polyolefin pipe is fusion-bonded via a polyolefin joint, a silicon compound such as polysilane or polysiloxane is present on the surface of the pipe or the joint and heated. In addition, there is disclosed a method of fusing without reducing the fusing strength even when deposits (eg, sand, polyolefin oxide film, etc.) are present on the surface of the pipe or joint.

  Usually, polysilane or polysiloxane contains a hydrogen atom directly bonded to a silicon atom, a hydroxyl group, an oxygen atom, a chlorine atom or the like in a polymer chain or at a polymer terminal. However, when such a silicon-containing polymer containing a hydrogen atom, a hydroxyl group, an oxygen atom, a chlorine atom or the like is used as a fusing agent, the adherend may not be reliably and firmly fused.

  In order to improve or improve such fusing properties, it has also been proposed to modify silicon-containing polymers. Japanese Patent Application Laid-Open No. 2003-82325 (Patent Document 2) discloses a fusion agent composed of a polysilane derivative in which the terminal of polysilane is blocked with a blocking agent, and a method for bonding adherends using the fusion agent Is disclosed.

  When the fusing agent disclosed in this document is used, the adherend can be strongly fused more easily than polysilane having a general end not blocked. However, since polysilane is usually colorless and transparent, it is difficult to visually recognize whether or not it adheres or intervenes at the fusion interface. In particular, this difficulty in visual recognition is due to the fact that the color of the adherend (or fusion interface) such as a gas pipe (polyolefin pipe) is colored (especially dark) or in dark places such as at night. This is especially true when Therefore, in practice, polysilane coating and spraying on the fusion interface must be performed sensibly, and depending on the mode of work (for example, work in a dark place or a narrow place), the fusion interface may be applied to the fusion interface. In some cases, an amount of polysilane effective for fusing cannot be interposed. In such a case, it is necessary to use a large amount of polysilane in order to ensure sufficient fusion strength, or even if such a large amount of polysilane is used, fusion is required. In some cases, the polysilane cannot be effectively adhered to the site, or uneven adhesion of the polysilane at the fusion interface causes unevenness of the fusion strength, or rather the fusion property is lowered.

  Therefore, further improvement in workability and fusing property when polysilane is used as a fusing agent is required.

  In Patent Document 2, polysilanes whose ends are blocked have both moderate thermal decomposability and stability, and because of their high stability, the adherend is less than polysilanes whose ends are not blocked. However, there is no description about the characteristics and properties of the polysilane whose end is blocked.

WO98 / 46928 Publication (Claims) JP2003-82325A (Claims, paragraph [0053])

  Accordingly, an object of the present invention is to provide a fusion agent having excellent visibility, an injector containing (filled) the fusion agent, and a joining method using the fusion agent.

  Another object of the present invention is to provide a fusion agent capable of reliably joining adherends even in a small amount, an injector containing the fusion agent, and a joining method using the fusion agent.

  Still another object of the present invention is to provide a fusion agent capable of improving or improving workability in a dark place or a closed place, an injector including the fusion agent, and a joining method using the fusion agent.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that a fusion agent composed of a polysilane whose end is blocked with a blocking agent and a colorant (or a dye or pigment, for example, a fluorescent dye). The present invention has been completed by finding that it has excellent visibility and can adhere the adherend reliably even in a small amount.

  That is, the fusing agent (fusing agent composition) of the present invention contains polysilane (A) whose ends are blocked and a colorant (B). In such a fusing agent, the polysilane (A) may be a linear polysilane having a relatively low molecular weight (for example, a weight average molecular weight of 5000 or less) whose ends are blocked. In addition, the polysilane (A) may be liquid at normal temperature (and normal pressure). Such a polysilane (A) is excellent in fusing ability, and is often high in compatibility with the colorant (B), so that the effect of improving visibility is high.

  In particular, the colorant (B) may contain a fluorescent dye (or a fluorescent colorant or a fluorescent pigment, for example, a coumarin fluorescent dye). In particular, in the fusion agent of the present invention, the polysilane (A) may be in a liquid state at room temperature, and the colorant (B) may be dissolved in the polysilane (A). Since such a fluorescent dye can improve the visibility efficiently, it is possible to maintain the fusion property at a high level. Such an effect can be obtained by using a colorant that can be dissolved in polysilane (A) such as a coumarin-based fluorescent dye ( There are many cases in B).

  In the fusion agent of the present invention, the ratio of the colorant (B) may be, for example, 1 part by weight or less with respect to 100 parts by weight of the polysilane (A). In the present invention, even with such a small amount, sufficient visibility can be imparted to the fusing agent and the fusing ability of the polysilane (A) is not impaired, so that the fusing ability and high visibility of the polysilane (A) are not impaired. Can be made compatible.

  As a typical fusing agent, polysilane (A) is a linear polyalkylarylsilane which is liquid at room temperature and whose end has a weight average molecular weight of 3000 or less, and the colorant (B) is Fusing agent which is a fluorescent dye, the colorant (B) is dissolved in the polysilane (A), and the proportion of the colorant (B) is 0.5 parts by weight or less with respect to 100 parts by weight of the polysilane (A) Etc. are included.

  The fusing agent of the present invention may further contain a solvent (C), and such a solvent (C) may be a gas at normal temperature. Typically, the fusion agent of the present invention further contains a gaseous solvent (C) at room temperature and is dissolved in a solvent (C) in which at least polysilane (A) is liquefied (for example, a solvent containing dimethyl ether). May be. In such a fusing agent containing the solvent (C), the ratio of the total amount of the polysilane (A) and the colorant (B) is, for example, 0.1 to 5 parts by weight with respect to 100 parts by weight of the solvent (C). It may be a degree.

  The present invention includes an injector (spray or the like) filled with the above-mentioned fusion agent containing a solvent (C) that is gaseous at room temperature. Such an injector is typically filled with a fusing agent containing polysilane (A) whose end is blocked, the colorant (B), and a solvent (C) which is gaseous at room temperature. In addition, the injector may be filled with a fusing agent in a state where at least polysilane (A) is dissolved in the liquefied solvent (C).

  The present invention also includes a method of joining the adherends by heating by interposing (or adhering) the above-mentioned fusion agent between the fusion interfaces (or fusion interfaces) of the adherends. In this joining method, spraying or spraying may be performed using the injector, and the fusion agent may be interposed between the fusion interfaces. In the adherend, the fusion interface may be colored. In the method of the present invention, since a fusion agent having excellent visibility is used, even if such a fusion interface is colored, it can be joined efficiently.

  Further, in the above method, a fluorescent dye (or fluorescent pigment or fluorescent brightening agent) is used as the colorant (B), and a fusion agent is interposed or adhered between the fusion interfaces under irradiation of light (for example, ultraviolet rays). May be. In such a method, the adhesion state of the fusing agent can be confirmed by light emission from the fluorescent dye, and the fusing agent can be used efficiently.

  In the present invention, since a fusion agent composed of a polysilane derivative is used, various thermoplastic resins can be reliably and effectively fused even if impurities such as sand adhere to the fusion interface. In addition, the fusing agent of the present invention can be applied to various joining methods as well as the joining method of the pipe body via the joint, and the joining strength of the adherend can be improved.

  Since the fusion agent of the present invention is composed of a polysilane whose end is blocked and a colorant (for example, a fluorescent dye), it is usually composed of a polysilane that is colorless or light-colored. Excellent visibility. For this reason, in the fusion agent of the present invention, it is easy to confirm whether or not the polysilane adheres to the fusion interface of the adherend, and the adherend is reliably bonded even in a small amount without using a large amount of polysilane. it can. Moreover, since the fusion agent of the present invention can easily confirm the application state of the polysilane at the fusion interface with the colorant, the workability in a dark place (such as at night) or closed place can be improved or improved.

FIG. 1 is a schematic cross-sectional view for explaining a joining method in Examples and Comparative Examples. FIG. 2 is a partial schematic cross-sectional view showing a fused portion in the schematic cross-sectional view of FIG. 1. FIG. 3 is a schematic cross-sectional view showing a peel test method in Examples and Comparative Examples.

  The fusing agent (composition, fusing agent composition, fusing composition) of the present invention contains polysilane (A) whose ends are blocked and a colorant (B).

[Polysilane (A)]
Examples of polysilane (A) include linear, branched, or cyclic polysilane. Of these structures, from the viewpoint of fusibility, typically, a linear or cyclic polysilane may be suitably used.

Such a polysilane can be represented by the following formula (1), for example, and is composed of a polysilane unit and inert groups Z ¹ and Z ² that block the ends of the polysilane unit.

(Wherein R ¹ and R ² are the same or different from each other and represent a hydrocarbon group, Z ¹ and Z ² are the same or different from each other and represent an inert group, and Z ¹ and Z ² are bonded to each other to form a ring. And n represents a positive integer.)
In the formula (1), the hydrocarbon group represented by R ¹ and R ² is preferably an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group. Examples of the alkyl group include C _1-10 alkyl groups (preferably C _1-6 alkyl groups, more preferably C _1-4 alkyl groups) such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, and pentyl. It is done. Examples of the cycloalkyl group include C _5-10 cycloalkyl groups (preferably C _5-8 cycloalkyl groups) such as cyclopentyl, cyclohexyl, and methylcyclohexyl. Examples of the aryl group include C _6-20 aryl groups (preferably C _6-10 aryl group, more preferably C _6-8 aryl group) such as phenyl, methylphenyl, dimethylphenyl, ethylphenyl, naphthyl and the like. R ¹ and R ² may be the same or different. When n is 2 or more, R ¹ or R ² may be the same or different groups (that is, may be a copolymer).

Representative combinations of R ¹ and R ² include, for example, (a) alkyl groups [eg, C _1-4 alkyl groups (particularly methyl groups)], (b) alkyl groups [eg, C _1-4 Alkyl groups (especially methyl groups)] and aryl groups (particularly phenyl groups), (c) aryl groups, and the like. Preferred combinations of R ¹ and R ² include (a) or (b) (In particular, combination (b)) and the like are included. By selecting a combination of R ¹ and R ² (further, the degree of polymerization n and the types of terminal groups Z ¹ and Z ² described later), polysilane (A) is liquid at room temperature while ensuring high fusion properties. It can be.

The inert groups Z ¹ and Z ² are the same or different and include an inert group such as a silyl group, an acetyl group, and a fluorine atom, and a silyl group is preferable.

In the formula (1), the silyl group constituting the inactive groups Z ¹ and Z ² is a silyl group in which all hydrogen atoms are substituted with an alkyl group or an aryl group, such as a trialkylsilyl group (trimethylsilyl, triethyl). Tri-C _1-10 alkylsilyl group such as silyl, tripropylsilyl, triisopropylsilyl, tributylsilyl, t-butyldimethylsilyl, preferably tri-C _1-6 alkylsilyl group, more preferably tri- _C1-4 alkylsilyl Groups), triarylsilyl groups (for example, tri-C _6-10 arylsilyl groups such as triphenylsilyl), dialkylarylsilyl groups (for example, diC ₁ such as dimethylphenylsilyl, diethylphenylsilyl, ethylmethylphenylsilyl). _-10 alkyl _{C 6-10} Arirushiri Group, preferably a _{di-C 1-6} alkyl _{C 6-8} aryl silyl group, more preferably a and di _{C 1-4} alkyl phenyl silyl group), alkyldiarylsilyl groups (e.g., methyl diphenyl silyl, ethyl diphenyl silyl, propyl diphenyl C _1-10 alkyldiC _6-10 arylsilyl group such as silyl, preferably C _1-6 alkyldiC _6-8 arylsilyl group, more preferably C _1-4 alkyldiphenylsilyl group, etc.).

When Z ¹ and Z ² are bonded to each other to form a ring, it becomes a cyclic polysilane. That is, the cyclic polysilane has a structure in which the inert groups Z ¹ and Z ² do not exist in the formula (1) and the ends are directly bonded to each other.

In the formula (1), n (degree of polymerization) can be selected from the range of about 1 to 5000 (for example, 1.5 to 2000), for example, 1 to 1000 (for example, 1.5 to 500), preferably It may be about 2 to 300 (for example, 2.5 to 200), more preferably about 3 to 100 (for example, 4 to 50). In particular, n in the cyclic polysilane (when Z ¹ and Z ² are bonded to each other to form a ring) is, for example, 2 to 12, preferably 3 to 10, and more preferably about 4 to 8. Good.

In particular, in Formula (1), n may be 2-30 (for example, 3-20), preferably 3-15 (for example, 4-12), more preferably about 5-10. Such a relatively low degree of polymerization polysilane (particularly chain polysilane) is excellent in fusibility and is often in a liquid form at room temperature, depending on the type of R ¹ and R ² . Moreover, although depending on the type of the colorant (B), the colorant (B) often has a characteristic that it can be easily dispersed (especially dissolved) in the polysilane (A). Therefore, even if it combines with a coloring agent (B) in a fusing agent, it is easy to improve visibility reliably without impairing fusing property.

Representative polysilanes (A) include (1) linear polyalkylalkylsilanes whose ends are blocked (corresponding to the combination of (a) above), and (2) linear polyalkylarylsilanes whose ends are blocked (Corresponding to the combination of (b)), (3) linear polydiarylsilanes whose ends are blocked (corresponding to the combination of (c)) and the like are included, and in particular, from the viewpoint of fusibility, (2) A linear polyalkylarylsilane whose end is blocked may be suitably used. Examples of the group (blocking group) for blocking the terminal include Z ¹ and Z ² exemplified above (for example, trialkylsilyl group, dialkylarylsilyl group, etc.).

  In addition, the weight average molecular weight of polysilane (A) can be selected from the range of 200-1 million, for example, is 300-100000 (for example, 400-50000), More preferably, it is about 500-10000 (for example, 700-7000). May be. In particular, the number average molecular weight of the polysilane (A) is about 5000 or less (for example, 300 to 4000), preferably about 3000 or less (for example, 400 to 2500), more preferably about 2000 or less (for example, 500 to 1500). Also good. Similarly to the above, the low molecular weight polysilane (A) is suitable because it is easy to impart a good balance between fusing property and visibility in the fusing agent.

As long as the performance as a fusing agent is not impaired, the polysilane may have a unit in which a part of R ¹ and R ² is a hydrogen atom, a hydroxyl group, a chlorine atom, a bromine atom, an iodine atom, or the like. Good.

  Moreover, although it is preferable that the terminal of polysilane is completely blocked, as long as the performance as a fusing agent is not impaired, a part of terminal may not be blocked. The terminal blocking ratio of polysilane is better as long as it does not hinder the fusibility, and may be 50 to 100%, preferably 75 to 100%, and more preferably about 90 to 100%.

  Polysilane (A) may be used alone or in combination of two or more.

  The polysilane (A) may be solid or liquid at normal temperature (for example, about 15 to 30 ° C.). In particular, the polysilane (A) is preferably liquid at normal temperature (and normal pressure). Such a liquid polysilane (A) is excellent in fusibility (fusing ability) and, as will be described later, by combining with a soluble colorant (B), visibility in fusing is further improved. Since it can improve further, it is suitable.

The liquid polysilane (A) is selected from, for example, the types of R ¹ and R ² in the formula (1) [for example, at least one of R ¹ and R ² is an alkyl group (for example, a lower alkyl such as a methyl group). Etc.) or by relatively reducing the polymerization degree and molecular weight of the polysilane.

In addition, polysilane (A) can be manufactured using the method of Unexamined-Japanese-Patent No. 2003-82325 etc., for example, (i) Polysilane (polysilane unit) by which the terminal is not blocked, and the said inactive as a blocking agent A method of reacting silyl compounds corresponding to the groups Z ¹ and Z ² (for example, monohalosilanes, silyl triflates, etc.), and (ii) halosilanes corresponding to polysilanes whose ends are not blocked (for example, dihalosilanes) It can be obtained by a method of reacting (polymerizing) with monohalosilanes.

[Colorant (B)]
As the colorant (dye, pigment, dyeing pigment, pigment), it is only necessary to improve the visibility in the fusion agent, and includes inorganic colorant (inorganic pigment or inorganic dye), organic colorant (organic pigment or organic dye), and the like. It is. The dye may be water-soluble or oil-soluble. Inorganic pigments include black pigments [carbon black (for example, acetylene black, lamp black, thermal black, furnace black, channel black, ketjen black, etc.)], white pigments [titanium-based white pigments (titanium oxide, etc.), zinc White pigments (such as zinc oxide and zinc sulfide), complex white pigments (such as lithopone), extender pigments (such as magnesium silicate, calcium carbonate, barium sulfate, aluminum hydroxide, and bentonite)], yellow pigments such as chrome yellow, oxidation Examples include red pigments such as iron red, orange pigments such as molybdate orange, green pigments such as chrome green, blue pigments such as bitumen, purple pigments such as manganese violet, cadmium pigments, lead pigments, and cobalt pigments. . Organic dyes (organic dyes) include azo dyes (pigment yellow, hansa yellow, benzidine yellow, permanent red, brilliant carmine 6B, etc.), phthalocyanine dyes (phthalocyanine blue, phthalocyanine green, etc.), lake dyes and pigments (Lake red, watch chan red, etc.), cyanine dyes, carbazole dyes, pyromethene dyes, anthraquinone dyes, naphthoquinone dyes, quinacridone dyes, perylene dyes, perinone dyes. , Isoindoline dyes, pigments, dioxazine dyes, selenium dyes and the like. The dye includes a functional dye (functional dye) such as a fluorescent dye (fluorescent dye).

  The colorants may be used alone or in combination of two or more.

  Of these colorants, fluorescent dyes are preferable from the viewpoints of being able to be dyed (or colored) with a small amount and excellent visibility at night. Therefore, the colorant (B) may contain at least a fluorescent dye. Hereinafter, the fluorescent dye (phosphor, luminescent pigment, fluorescent agent, fluorescent colorant) will be described in detail.

  The emission color of the fluorescent dye is not particularly limited, and may be any of blue, red, yellow, green, and the like, and may be appropriately selected according to the color of the adherend. For example, when the adherend is colored yellow, non-yellow fluorescent dyes such as red, blue, and green may be suitably used. The fluorescent dye may be a brightener (fluorescent brightener).

  Specific fluorescent dyes may be inorganic fluorescent dyes [for example, alkaline earth metal compounds (for example, inorganic acid salts of alkaline earth metals such as barium silicate, calcium tungstate, calcium phosphate, etc.)]. However, from the viewpoint of compatibility with polysilane (A), an organic fluorescent dye may be preferably used.

  Representative organic fluorescent dyes include, for example, oxazole compounds [or oxazole derivatives, and the same, for example, benzoxazole compounds such as 4,4′-bis (benzoxazol-2-yl) furan, etc.], stilbene compounds, and the like. Compounds [eg, 4,4′-bis (diphenyltriazinyl) stilbene, 4,4′-bis (benzoxazol-2-yl) stilbene, etc.], naphthalimide compounds (eg, N-methyl-5-methoxy) Naphthalimide, etc.), benzimidazole compounds, rhodamine compounds (eg, rhodamine B, rhodamine 6G, etc.), thiophene compounds [eg, 2,5-bis (5′-t-butylbenzoxazolyl-2 ′) Thiophene, 2,5-bis (6,6'-bis (tert-butyl) -benzoxa Ur-2-yl) thiophene, etc.], phthalic acid compounds (diethyl-2,5-dihydroxyterephthalate, o-phthalaldehyde), thiazine compounds, coumarin compounds, oxazine compounds, styrene biphenyl compounds, pyrazolone compounds Compounds, distyryl biphenyl compounds, imidazole compounds, imidazolone compounds, triazole compounds, pyridine compounds, pyridazine compounds, quinacridone compounds, oxacyanine compounds, carbostyril compounds, methine compounds, azomethine compounds, Examples include xanthene compounds.

  Fluorescent dyes may be used alone or in combination of two or more.

  Of these fluorescent dyes, a coumarin compound (coumarin derivative) may be particularly preferably used. The coumarin compound is excellent in compatibility (or solubility) with respect to polysilane (A) (especially low molecular weight (or low polymerization degree) or liquid polysilane (A)) among fluorescent dyes (fluorescent pigments). Therefore, even a small amount can efficiently impart high visibility to the fusing agent. Therefore, the ratio of the colorant (B) in the fusing agent can be reduced, and the high fusing property and excellent fusing property of the polysilane (A) can be efficiently realized.

Examples of the coumarin compound (coumarin fluorescent dye) include, for example, coumarin, hydroxycoumarins (for example, alkyl-hydroxycoumarins such as 4-methyl-7-hydroxy-coumarin), aminocoumarins {for example, alkyl-aminocoumarin [ for example, alkyl, such as 4-methyl-7-diethylamino coumarin - substituted amino coumarin (e.g., alkyl -N, N-dialkylamino coumarin, preferably _{C 1-10} alkyl -N, _{N-di-C 1-10} alkylamino coumarin More preferably C _1-4 alkyl-N, N-diC _1-4 alkylaminocoumarin)], aryl-aminocoumarins [eg aryl-aminocoumarins such as 3-phenyl-7-aminocoumarin; Phenyl-7- (imino-1′3′5′-triazine-2 '-Diethylamino-4'-chloro) -coumarin, 3-phenyl-7- (imino-1'3'5'-triazine-2'-diethylamino-4'-methoxy) -coumarin, 3-phenyl-7- ( Aryl such as 4-methyl-5-phenyl-1,2,3-triazol-2-yl) coumarin, 3-phenyl-7- (2H-naphtho [1,2-d] -triazol-2-yl) coumarin -Substituted aminocoumarin] and the like. The coumarin compounds may be used alone or in combination of two or more.

  The fluorescent dye usually absorbs ultraviolet rays and emits visible light. The absorption wavelength of such a fluorescent dye may be about 300 to 420 nm, preferably 320 to 410 nm, more preferably about 330 to 400 nm (for example, 340 to 400 nm) at the peak wavelength.

  In the fusing agent, the colorant (B) is preferably used in a dissolved state. As an aspect used in a dissolved state, an aspect in which it is dissolved in the liquid polysilane (A) at the normal temperature, an aspect in which it is dissolved in a solvent (C) described later, and the like are exemplified. In particular, the colorant (B) is preferably at least soluble in the polysilane (A). If the colorant (B) can be dissolved, the degree of adhesion of the polysilane (A) and the degree of coloring (light emission) can be matched or matched with high accuracy at the fusion interface of the adherend, and uniform. Adhesion of polysilane (A) can be easily realized. However, it seems that polysilane (A) is usually difficult to dissolve the colorant (B), probably because the end is blocked. Also from such a viewpoint, a colorant (B) that can be dissolved in polysilane (A) such as a fluorescent dye [for example, a coumarin compound (coumarin fluorescent dye)] can be preferably used.

  In the fusion agent of the present invention, the ratio of the colorant (B) can be selected according to the type of the colorant (B), and is 0.001 to 20 parts by weight (for example, 100 parts by weight of the polysilane (A)). , 0.002 to 18 parts by weight), for example, 0.005 to 10 parts by weight (for example 0.007 to 5 parts by weight), preferably 0.01 to 3 parts by weight (for example 0 0.02 to 2 parts by weight).

  In particular, when the colorant (B) contains a fluorescent dye, the ratio of the colorant (B) is relatively small, for example, 10 parts by weight or less (for example, 0.001 with respect to 100 parts by weight of the polysilane (A)). ˜7 parts by weight), preferably 5 parts by weight or less (eg, 0.005 to 4 parts by weight), and more preferably 3 parts by weight or less (eg, 0.01 to 2 parts by weight).

  The ratio of the colorant (B) is preferably large from the viewpoint of visibility, but if it is too large, the relative ratio of the polysilane (A) in the fusing agent becomes small, and the fusing property may be lowered. is there. On the other hand, from the viewpoint of such fusibility, it is preferable to reduce the ratio of the colorant (B), but if it is too small, sufficient visibility may not be imparted to the fusing agent. Thus, although it is difficult to obtain a fusion agent that satisfies both visibility and fusion property at a high level, as described above, by selecting the type of polysilane (A) or colorant (B), Even a very small amount can provide high visibility. In such a case, the ratio of the colorant (B) (particularly, a fluorescent dye such as a coumarin compound) is, for example, 2 parts by weight or less (for example, 0.001-1) with respect to 100 parts by weight of the polysilane (A). 0.5 parts by weight), preferably 1 part by weight or less (eg, 0.005 to 0.7 parts by weight), more preferably 0.5 parts by weight or less (eg, 0.01 to 0.4 parts by weight), especially It may be about 0.3 parts by weight or less (for example, 0.05 to 0.25 parts by weight).

[Other ingredients]
The fusing agent of the present invention may contain a reaction accelerator as necessary. Examples of the reaction accelerator include peroxides (benzoyl peroxide, t-butyl perbenzoate, di-t-butyl peroxide, etc.), azo compounds (azobisisobutyronitrile, dimethylazoisobutyrate, benzenediazonium). Chloride), persulfates (ammonium persulfate, potassium persulfate, sodium persulfate, etc.), carbonyl compounds (benzophenone, benzyl, benzoin ethyl ether, 4-N, N-dimethylamino-4′-methoxybenzophenone, etc.), organic Compounds that generate radicals by heat or light such as sulfur compounds (dibutyl sulfide, dibenzyl sulfide, decyl phenyl sulfide, etc.) (radical generators), acids (fatty acids such as acetic acid and propionic acid, p-toluenesulfonic acid, etc. Sulfonic acids , Aromatic carboxylic acids such as benzoic acid, inorganic acids such as hydrochloric acid), bases (aliphatic amines such as triethylamine, aromatic amines such as aniline, heterocyclic amines such as pyridine), sensitizers (for example, Quinones such as anthraquinone and benzoquinone, pyrenes such as pyrene and 1-nitropyrene, aromatic hydrocarbons such as acenaphthene, fluorene and biphenyl, and amines such as acridone). These reaction accelerators may be used alone or in combination of two or more.

  The proportion of the reaction accelerator may be about 0.1 to 20 parts by weight, preferably about 0.5 to 10 parts by weight, and more preferably about 1 to 5 parts by weight with respect to 100 parts by weight of the polysilane (A). .

  In addition, the fusion agent of the present invention may contain a conventional additive or the like as long as the fusion property and visibility are not impaired, but in order to ensure high fusion property, The solid content of the agent may be substantially composed of only the polysilane (A) and the colorant (B) (and the reaction accelerator if necessary). For example, the ratio of the total amount of the polysilane (A) and the colorant (B) in the fusing agent (or solid content constituting the fusing agent) is 90% by weight or more (for example, about 93 to 100% by weight), preferably Is 95% by weight or more (for example, about 97 to 100% by weight), more preferably 98% by weight or more (for example, about 98.5 to 100% by weight), particularly 99% by weight or more (for example, 99.5 to 100% by weight). %)).

[Solvent (C)]
The fusing agent of the present invention may contain a solvent. The solvent only needs to be able to dissolve or disperse the solid component of the fusing agent (polysilane (A), colorant (B), etc.), but can dissolve at least one selected from polysilane (A) and colorant (B). In particular, a solvent capable of dissolving at least polysilane (A) (more preferably polysilane (A) and colorant (B)) is preferable.

  Specific examples of the solvent include hydrocarbons (for example, aliphatic hydrocarbons such as pentane, hexane, and heptane, alicyclic hydrocarbons such as cyclohexane, and aromatic hydrocarbons such as benzene, toluene, and xylene. Etc.), alcohols (alkanols such as methanol, ethanol and propanol), ethers (eg cyclic ethers such as dioxane and tetrahydrofuran), ketones (eg chain ketones such as acetone and ethyl methyl ketone) , Cyclic ketones such as cyclohexanone), esters (eg, acetate esters such as ethyl acetate and butyl acetate), diols (alkane diols such as ethylene glycol and propylene glycol, polyoxyethylene glycol, etc.), cellosolves (Methyl cello Lube, ethyl cellosolve), and the like carbitol (such as carbitol). You may use a solvent individually or in combination of 2 or more types.

  The solvent includes a gas solvent at normal temperature [and / or normal pressure (1 atm)], that is, a solvent that becomes liquid under pressure (and / or low temperature) (a solvent that becomes a liquefied gas or a compressed gas). . Typically, the fusing agent of the present invention contains a gaseous solvent (C) at room temperature and may be dissolved in a solvent (C) in which at least polysilane (A) is liquefied. Such a solvent acts as a propellant and easily volatilizes (or vaporizes) under normal pressure (and normal temperature), so that dripping of the fusion agent at the fusion interface can be suppressed or prevented. On the other hand, when only a polysilane (A) is used, if such a volatile solvent is used, there is a possibility that the visibility at the fusion interface is rather lowered. However, with the fusion agent of the present invention, such visibility is reduced. Will not be damaged. Therefore, the fusing agent can be reliably and uniformly applied to the fusing interface without waste, and the workability in fusing can be further improved.

Such a solvent (propellant) may be any solvent having a boiling point lower than room temperature (for example, about 15 to 30 ° C.). For example, nonpolar or nonpolar organic solvents [for example, hydrocarbons (for example, C _1-4 alkanes such as propane, n-butane and isobutane)], polar organic solvents (for example, dimethyl ether), inorganic solvents (for example, carbon dioxide, nitrogen, nitrous oxide, oxygen, ammonia and the like) and the like. It is done. These normal and gaseous solvents may also be used alone or in combination of two or more. Further, a solvent that is gaseous at normal temperature and a solvent that is liquid at normal temperature may be combined.

Among these, a solvent capable of dissolving polysilane (A) (and colorant (B)) such as dimethyl ether is preferable. Therefore, the solvent may contain at least dimethyl ether, and dimethyl ether may be combined with another solvent. The other solvent to be combined with dimethyl ether is not particularly limited, and can be selected from the above-mentioned solvents excluding dimethyl ether. For example, a solvent that is a gas at normal temperature (for example, C _1-4 alkane, carbon dioxide, etc.) and a boiling point are compared. Low solvent (for example, C _5-8 alkane such as hexane, methanol, acetone, etc.).

  When dimethyl ether is combined with another solvent, these ratios are the former / the latter (weight ratio) = 99/1 to 10/90, preferably 97/3 to 30/70, more preferably 95/5 to 50 /. About 50 (for example, 90 / 10-60 / 40) may be sufficient.

  The liquefaction of the solvent (or the fusing agent) may be performed by cooling the fusing agent to a temperature lower than the boiling point of the solvent, but is usually liquefied at least under pressure. Therefore, a fusing agent containing a solvent that is liquid at normal temperature is usually filled in a container (such as a spray can) in a liquefied state (for example, a state in which the solvent is liquefied by pressurization or compression). In such a fusing agent, the pressure (filling pressure) is, for example, 0.5 MPa or less (for example, 0.1 to 0.5 MPa, preferably 0.3 to 0.45 MPa, and more preferably 0.3 MPa. About 0.4 MPa).

  In the fusing agent (fusing agent composition) containing the solvent (C), the ratio of the total amount of the polysilane (A) and the colorant (B) is, for example, 0.01 with respect to 100 parts by weight of the solvent (C). To 20 parts by weight (for example, 0.03 to 15 parts by weight), preferably 0.05 to 10 parts by weight (for example, 0.07 to 7 parts by weight), more preferably 0.1 to 5 parts by weight (for example, 0.2 to 4 parts by weight), particularly 0.3 to 3 parts by weight (for example, 0.5 to 2 parts by weight).

  The fusing agent of the present invention can be used as a fusing improver that improves the fusing strength of an adherend by adhering to the fusing interface for fusing. As a bonding method using the above-mentioned fusing agent, for example, a fusing agent is interposed (or adhered) at the fusion interface (or bonding interface) of the adherend, and the fusion interface (or bonding interface) of the adherend is used. Examples include a method of bringing them into contact with each other and heating.

Examples of the adherend (or the component constituting the adherend) include, for example, an olefin resin [C _2-10 olefin alone or copolymer (polyethylene (for example, high density polyethylene, medium density polyethylene, low density polyethylene). Etc.), polypropylene, poly 1-butene, polymethylpentene-1, polyisoprene, ethylene-propylene copolymer, etc.), copolymer of olefin and copolymerizable monomer (for example, ethylene-vinyl acetate copolymer) Polymers, ethylene- (meth) acrylic ester copolymers, etc.), modified polyolefins, etc.], styrene resins [polystyrene (GPPS), high impact polystyrene (HIPS), acrylonitrile-styrene copolymers (AS resin), acrylonitrile. -Butadiene-styrene block copolymer (ABS resin), Butae AXS resins using various rubbers X instead of rubber], polyester resins (polyalkylene arylates such as polyethylene terephthalate and polybutylene terephthalate, or copolyesters thereof), polycarbonate resins (such as bisphenol A polycarbonate), Acrylic resins (polymethyl methacrylate, methyl methacrylate-styrene copolymers, etc.), chlorine-containing vinyl resins (polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, vinylidene chloride-vinyl acetate copolymers, etc.), Polyamide resin (nylon 6, nylon 66, nylon 610, nylon 612, nylon 11, nylon 12, etc.), polyacetal resin (polyoxymethylene etc.), polysulfone resin (polysulfone, polyethersulfone etc.) Polyphenylene-based resin (polyphenylene oxide, polyphenylene sulfide, etc.) resins such as (in particular, thermoplastic resin) can be mentioned. The adherend may be formed of one kind or different resins, or may be formed of a polymer alloy composed of a plurality of resins.

  The adherend (or fusion interface) may be colored. In this invention, even if it is a colored adherend, adhesion of the fusion agent at the fusion interface can be easily confirmed by the colorant (B) (particularly, fluorescent dye).

  The shape of the adherend is not particularly limited, and examples thereof include a two-dimensional structure (film, sheet, plate, etc.), a three-dimensional structure (eg, tube, bar, tube, leather, hollow article, etc.) . Furthermore, the adherend may be a molded body (for example, a pair of pipes and joints) that can be fitted or attached to each other.

  A pretreatment may be applied to the fusion interface of the adherend. Pretreatment includes, for example, removal of oxide film at the interface by scraping (removal), removal of adherents such as fine particles and sand generated by scraping, corona discharge treatment, plasma discharge treatment, ultraviolet irradiation Processing. These pretreatments may be used alone or in combination of two or more.

  The fusing agent can be applied to the fusing interface by a conventional method such as brushing, spraying (or spraying or jetting), or dipping. In the present invention, a spray is particularly suitable from the viewpoint of workability. You may use it.

  Spraying can usually be performed using a fusing agent containing a solvent (C). In particular, in spraying, a container (or an injector) filled with the above-mentioned fusing agent containing a solvent (C) that is gaseous at normal temperature in a liquefied state may be suitably used. That is, the injector is filled with a fusing agent containing the liquefied solvent (C). Such an injector is typically filled with a fusing agent (a fusing agent as a propellant) in a state where at least polysilane (A) is dissolved in a liquefied solvent. As the container, an injector having an injection port for injecting or spraying a fusing agent (liquefied fusing agent) such as a spray can (or spray container) can be used. As the solvent (C), as described above, a solvent containing dimethyl ether can be suitably used. Such a liquefied gaseous fusing agent is very useful because it can be easily applied at the fusing interface and can effectively prevent dripping at the fusing interface.

  In the above method, a fluorescent dye may be used as the colorant (B), and a fusion agent may be interposed or adhered between the fusion interfaces under light irradiation. In such a method, since the fusion agent can be applied to the fusion interface while confirming the adhesion state of the fusion agent by light emission from the fluorescent dye, uniform adhesion of the fusion agent can be realized more efficiently. The light to be irradiated (or light source) can be selected according to the absorption wavelength of the fluorescent dye, but usually at least ultraviolet light or ultraviolet light [for example, 200 to 500 nm, preferably 250 to 450 nm, more preferably 300 to 420 nm (for example, , 320 to 400 nm)].

The adhesion amount of the fusion agent at the fusion interface may be small, for example, 0.1 to 50 g, preferably 1 to 30 g, more preferably 2 with respect to 1 m ² of the fusion interface in terms of polysilane (A). -10g may be sufficient. The fusing agent may be applied to both the adherends or the interface of one member. In addition, when the fusion agent contains a solvent, it is usually preferable to remove the solvent after application to the fusion interface or bonding interface, but as described above, if a liquefied gas or the like is used as the solvent, Such a solvent removal operation is not required.

  In the bonding method, the heat source can be selected according to the bonding method, and examples thereof include heat generation by electrical resistance, hot air, heat generation by friction, and heat generation by molecular motion. Further, during the heating, the adherend may be pressurized to press the fusion interface.

  The joining method includes joining methods of adherends via joints (for example, electrofusion method (EF method), heat fusion method (HF method), butt fusion, socket fusion, saddle fusion, etc.), It can be applied in various joining methods (for example, hot plate welding, hot air welding, impulse welding, vibration welding, spin welding, high frequency welding, induction heating welding, ultrasonic welding, etc.).

  The fusing temperature and fusing time in the joining method can be adjusted according to the glass transition temperature and wettability of the adherend, for example, the temperature is 150 to 300 ° C., preferably 170 to 250 ° C., more preferably 180 to It is about 220 ° C. The fusing time is 1 second to 10 minutes, preferably 10 seconds to 5 minutes, and more preferably about 20 seconds to 3 minutes.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

  The electrofusion method (EF method) was performed using the fusing agents obtained in the examples and comparative examples, and the pipe bodies were joined via joints.

  In addition, as shown in FIG.1 and FIG.2, the EF method in an Example and a comparative example is the bonding agent layer 3 in a joining area | region among edge part outer surfaces with a pair of gas pipes (polyolefin pipe) 2a, 2b. The joining region is disposed in the EF joint 1, the heating wire 4 disposed in the vicinity of the inner periphery of the EF joint 1 is energized, the EF joint 1 and the gas pipe 2 are joined, and a joining member Got.

Furthermore, the test (peel test) which measures the joint strength of the said joining member using a part of said joining member as a test piece was done. In the peel test, as shown in FIG. 3, the joint rod 15 was welded to the end of the EF joint 11, and the 180 ° peeling or breaking strength was measured. In addition, the connecting rod 15 and the gas pipe 12 are pulled, and the difference between the length of the bonded portion at the time of fusion (the heating width (L ₁ ) by the heating wire 4) and the length L ₂ of the bonded portion after the pull (L It confirmed the bonding state by measuring the maximum load value at ₁ -L ₂₎ and tension.

  In Examples, the number average molecular weight of polysilane was measured in terms of polystyrene by gel permeation chromatography (“GPC-8220” manufactured by Tosoh Corporation).

Example 1
A polymethylphenylsilane whose end is blocked with a dimethylphenylsilyl group (that is, in the formula (1), the combination of R ¹ and R ² is a combination of a methyl group and a phenyl group, and Z ¹ and Z ² are 0.2 g of coumarin-based fluorescent dye (Hakkol P, Showa Chemical Industry Co., Ltd.) was added to 100 g of polysilane that is a dimethylphenylsilyl group, weight average molecular weight 1120, liquid), and the mixture was stirred and dissolved. 2 g of this polysilane mixture was dissolved in 200 g of liquefied dimethyl ether (DME) and filled into a spray can (filling pressure 0.4 MPa) to prepare a spray can.

  Then, in a dark place assuming nighttime, spray the contents of the spray can while irradiating the joint (joint area) of the polyolefin tube (polyethylene tube, colored deep yellow) appropriately with ultraviolet light (375 nm). did. In addition, although DME which is a solvent component volatilized instantaneously with spraying, since the spray contents emitted light by light irradiation, spraying was performed while checking the joint portion so that the degree of this light emission was uniform.

Thereafter, sand having a particle size of 106 μm or less was adhered to the fused portion of the polyethylene pipe at a rate of 0.1 g / cm ² , and energized for 110 seconds with an average clearance of 0.5 mm using a heating wire (average supply power of about 4 W / cm ² ), And the EF joint and the polyethylene pipe were joined. Using a test piece (width 10 mm, heating width L ₁ = 31 mm) obtained from the joint, a peel test was performed under conditions of a constant temperature (23 ° C.) and a constant tensile speed (50 mm / second). As a result of the peel test, it was confirmed that no breakage occurred on the fusion surface, the maximum load value was about 700 N, the joint rod portion was broken, and it had sufficient performance as a fusion agent. There was no problem in workability.

(Comparative Example 1)
A spray can was prepared in the same manner as in Example 1 except that the coumarin fluorescent dye was not used, and the spray and the EF joint were joined to the polyethylene pipe. Note that the spray did not emit light even when irradiated with ultraviolet light, and the application state of the contents of the spray can by light emission could not be confirmed, so it had to be sprayed sensuously toward the joint. Further, since dimethyl ether has high volatility and a very small amount of polysilane occupies the contents, it is difficult to confirm the application state of the contents by wetting. As a result of the peel test, a fracture occurred on the fusion surface, the maximum load value was about 50 N, and it was confirmed that the performance was not sufficient as a fusion agent.

  Although the fusion agent of the present invention is composed of polysilane, it has excellent visibility and can easily confirm the degree of adhesion of the polysilane at the fusion interface. In particular, by adjusting the combination of the polysilane and the colorant and the blending amount of the colorant, even if the colorant is contained, the excellent fusion property by the polysilane can be efficiently exhibited. Therefore, the adhesive of the present invention is extremely useful because it can reliably bond the adherend even in a working environment such as at night or in a closed place.

DESCRIPTION OF SYMBOLS 1, 11 ... EF joint 2a, 2b, 12 ... Polyolefin pipe 3 ... Fusion agent layer 4 ... Heating wire 15 ... Joint rod

Claims (15)

  A fusion agent containing polysilane (A) whose ends are blocked and a colorant (B), further containing a gaseous solvent (C) at room temperature, and at least polysilane (A) liquefied (C Fusing agent dissolved in).   The fusing agent according to claim 1, wherein the polysilane (A) is a linear polysilane having a weight-average molecular weight of 5000 or less and having an end blocked.   The fusing agent according to claim 1 or 2, wherein the polysilane (A) is liquid at normal temperature.   The fusing agent according to any one of claims 1 to 3, wherein the colorant (B) contains a fluorescent dye.   The fusing agent according to any one of claims 1 to 4, wherein the colorant (B) contains a coumarin fluorescent dye.   The fusing agent according to any one of claims 1 to 5, wherein the polysilane (A) is liquid at normal temperature and the colorant (B) is dissolved in the polysilane (A).   The ratio of a coloring agent (B) is 1 weight part or less with respect to 100 weight part of polysilane (A), The fusing agent in any one of Claims 1-6.   The polysilane (A) is a linear polyalkylarylsilane that is liquid at room temperature and has a weight-average molecular weight of 3000 or less, which is blocked at the end, the colorant (B) is a fluorescent dye, and the colorant (B ) Is dissolved in the polysilane (A), and the ratio of the colorant (B) is 0.5 parts by weight or less with respect to 100 parts by weight of the polysilane (A). Dressing.   The fusing agent according to any one of claims 1 to 8, wherein the solvent (C) contains dimethyl ether.   The ratio of the total amount of polysilane (A) and a coloring agent (B) is 0.1-5 weight part with respect to 100 weight part of solvents (C), The fusing agent in any one of Claims 1-9 .   An injector filled with a fusion agent containing a polysilane (A) whose ends are blocked, a colorant (B), and a solvent (C) that is gaseous at room temperature, and at least the polysilane (A) is liquefied An injector that is filled with a fusing agent in a state dissolved in (C).   A method for joining an adherend by heating with the fusion agent according to any one of claims 1 to 10 interposed or adhered between the fusion interfaces of the adherend. Using the injector filled with the fusion agent according to claim 1, the fusion agent is interposed or adhered between the fusion interfaces of the adherend and heated by spraying or spraying. A method for joining adherends.   The joining method according to claim 12 or 13, wherein the fusion interface is colored.   The joining method according to any one of claims 12 to 14, wherein a fluorescent dye is used as the colorant (B) and a fusing agent is interposed or adhered between the fusing interfaces under light irradiation.

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