JP2007246797A - Deodorant pressure-sensitive adhesive and deodorant pressure-sensitive adhesive processed product prepared from the adhesive - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a deodorant pressure-sensitive adhesive free of toluene or xylene, and forming a pressure-sensitive adhesive layer having the function of adsorption and decomposition of external chemical substances such as formaldehyde, ammonia, amines, acetic acid and sulfides, and a deodorant pressure-sensitive adhesive processed product using the deodorant pressure-sensitive adhesive. <P>SOLUTION: The deodorant pressure-sensitive adhesive is characterized in being free of toluene and xylene, and contains (A) a copolymer having a hydroxy group and/or carboxy group prepared by radical polymerization of a radical polymerizable unsaturated monomer, (B) a curing agent having a functional group to react with hydroxy group and/or carboxy group and (E) a complex deodorant component prepared by the surface treatment of a chemical adsorption type deodorant component (D) such as an amino compound-carrying silicon dioxide compound (d1) with an iron compound (C). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a pressure-sensitive adhesive containing no toluene or xylene, and relates to a deodorant pressure-sensitive adhesive having a deodorizing function and a deodorant pressure-sensitive adhesive processed product using the pressure-sensitive adhesive.

Conventionally, in the field of solvent-based pressure-sensitive adhesives, a copolymer obtained by polymerizing a radical polymerizable monomer has been widely used as a resin component constituting the main component of the pressure-sensitive adhesive, and is polymerized in the presence of toluene or xylene. There were many things.
However, in recent years, solvent-based pressure-sensitive adhesives have come to require pressure-sensitive adhesives that do not contain toluene or xylene from the environmental aspect.

By the way, an adhesive processed product using an adhesive has been widely used for various purposes in the past, and is attached to an adherend, such as building material application, household appliance member application, wallpaper application, etc. There are also uses that are left indoors. Formaldehyde, ammonia, amines, acetic acid, sulfides, toluene, xylene and the like are not only disliked in terms of odor but are also considered as causative substances of so-called sick house syndrome. Therefore, it is desirable that various members constituting the house and other buildings and various products left in the room do not contain the aversion odor substance or the substances that cause the aversion odor substance.
However, it is almost impossible to exclude from the living environment any of the aversion odor substances or substances that cause the aversion odor substances. For example, the aversible odorous substance can be generated from food itself or a spoiled food, and the aversional odorous substance can also be generated from human or pet excrement.
Therefore, it seems that adhesive members that make up various components that make up houses and other buildings and various products that are left indoors are expected to have the function of adsorbing and decomposing external odorous substances. Came.

  Patent Document 1 (Japanese Patent Application Laid-Open No. 8-24206) discloses an antibacterial pressure-sensitive adhesive, and discloses the use of zirconium phosphate as a carrier for an inorganic antibacterial agent such as copper.

  Patent Document 2 (Japanese Patent Laid-Open No. 2000-281998) discloses an adhesive containing an aldehyde gas absorbent in which an amine compound is supported on silicon dioxide.

  Patent Document 3 (Japanese Patent Application Laid-Open No. 2004-51812) describes an invention for suppressing formaldehyde that can be generated via an adhesive processed product using an adhesive containing acetylacetone. However, an effect is not recognized in the reduction of an aversive odor substance.

  Patent Documents 4 to 8 describe that a reducing agent such as L-ascorbic acid and various iron compounds function as a deodorizing / deodorizing agent. However, although the interaction between these odorous substances and iron compounds is weak and durable, the degree of deodorizing function is insufficient.

In other words, the conventional adhesive processed products are excellent in the initial deodorizing property, but are largely divided into two types: a type with poor sustainability, or a type with poor initial deodorizing property, but with long lasting properties. . Therefore, the appearance of an adhesive processed product having excellent initial deodorizing properties and excellent deodorizing function has been desired.
JP-A-8-24206 JP 2000-281998 A JP 2004-51812 A JP-A-5-163647 JP 59-132937 A JP-A 63-275782 Japanese Patent Laid-Open No. 61-278349 JP-A-4-126153

  The present invention is a deodorant pressure-sensitive adhesive which does not contain toluene or xylene and can form a pressure-sensitive adhesive layer having a function of adsorbing and decomposing chemical substances such as external formaldehyde, ammonia, amines, acetic acid and sulfides. Another object of the present invention is to provide a deodorant adhesive processed product using the same.

The present invention relates to a copolymer (A) having a hydroxyl group and / or a carboxyl group obtained by radical polymerization of a radically polymerizable unsaturated monomer capable of forming a copolymer having a glass transition temperature of -80 to -10 ° C, a hydroxyl group. And / or a deodorant pressure-sensitive adhesive containing a curing agent (B) having a functional group capable of reacting with a carboxyl group and a composite deodorant component (E) and not containing toluene or xylene,
The composite deodorant component (E) is a polyamine compound-supported silicon dioxide compound (d1) having two or more primary amino groups, zirconium phosphate (d2), hydrous zirconium oxide (d3), and copper compound (d4) The present invention relates to a deodorant pressure-sensitive adhesive characterized in that the surface of at least one or more chemisorption deodorant compounds (D) selected from the group consisting of is treated with an iron compound (C).

  Moreover, this invention relates to the deodorizing adhesive as described in the said invention characterized by containing organic solvents other than toluene and xylene.

  The present invention also relates to the deodorant pressure-sensitive adhesive according to any one of the above inventions, wherein the iron compound (C) is a compound containing a divalent iron ion.

  In the present invention, the composite deodorant component (E) is obtained by surface-treating 0.5 to 5 parts by weight of the chemisorption deodorant compound (D) with 1 part by weight of the iron compound (C). The deodorant pressure-sensitive adhesive according to any one of the above inventions.

  The present invention also relates to the deodorant pressure-sensitive adhesive according to any one of the above inventions, wherein the copper compound (d4) is any one of copper carbonate, copper phosphate and copper hydroxide.

  Moreover, this invention contains 1-30 weight part of iron compounds (C), and 1-50 weight part of chemisorption type deodorant compounds (D) with respect to 100 weight part of copolymers (A). The deodorizing pressure-sensitive adhesive according to any one of the above-described inventions.

  Moreover, this invention relates to the deodorizing adhesive as described in any one of the said invention characterized by further containing tackifying resin (F).

  Furthermore, the present invention is described in the above invention, wherein the weight ratio of the copolymer (A) and the tackifier resin (F) is (A) / (F) = 90 / 10-60 / 40. This relates to a deodorant pressure-sensitive adhesive.

  Furthermore, the present invention relates to a deodorant pressure-sensitive adhesive product obtained by providing a deodorant pressure-sensitive adhesive layer formed from the deodorant pressure-sensitive adhesive described in any one of the above inventions on a substrate.

  Deodorant pressure-sensitive adhesive that does not contain toluene or xylene and can form a pressure-sensitive adhesive layer that has the function of adsorbing and decomposing chemical substances such as formaldehyde, ammonia, amines, acetic acid, sulfides, etc. And a deodorant adhesive processed product using the same.

The copolymer (A), which is the main component of the deodorant pressure-sensitive adhesive of the present invention, will be described. The copolymer (A) is obtained by radical polymerization of a radical polymerizable unsaturated monomer capable of forming a copolymer having a glass transition temperature of −80 to −10 ° C., and has a hydroxyl group and / or a carboxyl group.
The carboxyl group and hydroxyl group in the copolymer (A) have a function of increasing the cohesive force of the pressure-sensitive adhesive layer by reacting with the curing agent (B) described later. In particular, since the carboxyl group is effective in maintaining the activity of the iron compound (C) described later, the copolymer (A) preferably has a carboxyl group.
Examples of the carboxyl group-containing radical polymerizable monomer used for introducing a carboxyl group into the copolymer (A) include (meth) acrylic acid, maleic acid, and itaconic acid.
Examples of the hydroxyl group-containing radical polymerizable monomer used for introducing a hydroxyl group into the copolymer (A) include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and hydroxypropyl (meth) acrylate. Can be mentioned.

The copolymer (A) is a main component of the pressure-sensitive adhesive, and various other compounds having no carboxyl group or hydroxyl group so that the glass transition temperature of the copolymer (A) is -80 to -10 ° C. What is necessary is just to form a copolymer (A) by copolymerizing with a radically polymerizable unsaturated monomer. The glass transition temperature of the formed copolymer (A) is preferably −60 to −20 ° C.
The glass transition temperature of the copolymer (A) can be calculated by a known theoretical formula based on the glass transition temperature of the homopolymer of the radical polymerizable unsaturated monomer constituting the copolymer (A).
Other radical polymerizable unsaturated monomers having no carboxyl group or hydroxyl group include 2-ethylhexyl (meth) acrylate, n-butyl (meth) acrylate, ethyl (meth) acrylate, methyl (meth) acrylate, iso-butyl ( (Meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, n-decyl (meth) acrylate, n-dodecyl (meth) acrylate, lauryl (meth) acrylate, Examples include vinyl acetate, acrylonitrile, acrylamide, glycidyl methacrylate, and styrene.

The copolymer (A) can be obtained by radical polymerization of the above radical polymerizable unsaturated monomer in an organic solvent other than toluene and xylene according to a conventional method. As an organic solvent other than toluene and xylene, ethyl acetate, acetone, methyl ethyl ketone, and methyl isobutyl ketone can be used alone or in combination of two or more, and ethyl acetate is used alone in terms of reaction temperature. It is preferable.
As the polymerization initiator, a peroxide polymerization initiator or an azo polymerization initiator can be used.

  The copolymer (A) preferably has a weight average molecular weight in terms of polystyrene of gel permeation chromatography of 400,000 to 900,000, and more preferably 500,000 to 750,000. When the weight average molecular weight is less than 400,000, the heat-resistant performance and cohesive strength of the obtained pressure-sensitive adhesive processed product tend to decrease. On the other hand, when it exceeds 900,000, the pressure-sensitive adhesive strength and coating performance tend to decrease.

The deodorant pressure-sensitive adhesive of the present invention contains a curing agent (B) having a functional group capable of reacting with a carboxyl group or a hydroxyl group.
As such a curing agent (B), isocyanate compounds, epoxy compounds, aziridine compounds, metal chelate compounds and the like can be used.

Examples of the isocyanate compound include various polyisocyanate compounds. For example, various well-known various diisocyanates of aromatic, aliphatic or alicyclic can be mentioned.
Examples of aromatic diisocyanates include 1,5-naphthylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-diphenyldimethylmethane diisocyanate, 4,4′-dibenzyl isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, etc.
Aliphatic diisocyanates include butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, xylylene diisocyanate, m-tetramethylxylylene diene Isocyanate, dimerized isocyanate, etc., in which the carboxyl group of dimer acid is converted to an isocyanate group,
Examples of the alicyclic diisocyanate include cyclohexane-1,4-diisocyanate, isophorone diisocyanate, lysine diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, 1,3-bis (isocyanatemethyl) cyclohexane, methylcyclohexane diisocyanate, norbornane diisocyanate, and the like. Each is listed.
These isocyanate compounds are preferably used in an amount of 1.0 to 5.0 parts by weight, more preferably 1.5 to 3.0 parts by weight, based on 100 parts by weight of the copolymer (A).

The epoxy compound may be a compound containing two or more glycidyl groups, and examples thereof include glycerol polyglycidyl ether.
Examples of the aziridine compound include bishydroxymethylbutanol trisazilinylpropionate,
Examples of the metal chelate compound include metal chelate compounds such as aluminum, titanium, and zirconium.
The curing agent other than these isocyanate compounds is preferably used in an amount of 0.01 to 5.0 parts by weight, more preferably 0.1 to 1.0 parts by weight, based on 100 parts by weight of the copolymer (A). preferable.

Next, the composite deodorant component (E) used for the deodorant adhesive of this invention is demonstrated.
The composite deodorant component (E) is obtained by treating the surface of the chemisorption deodorant compound (D) with the iron compound (C).
The chemisorption type deodorant compound (D) has an immediate effect of the deodorization function, but the deodorization function is lowered when the adsorption site is filled with the odor substance. In other words, it has poor sustainability. The composite deodorant component (E) uses the adsorption function of the chemisorption deodorant compound (D), adsorbs odorous substances, and effectively adsorbs using the redox function of the iron compound (C). Since the decomposed odorous substance is decomposed, it is possible to satisfy both the immediate effect and the sustainability of the deodorizing function.
Mixing the chemisorption deodorant compound (D) and the iron compound (C) is considered to improve the immediate effect and sustainability of the deodorant function compared to using each of them alone. . However, in the case of mere mixing, since both are present independently, it is difficult to smoothly perform a series of cycles of adsorption, oxidation reduction, and decomposition and deodorization. Therefore, in order to satisfy both the immediate effect and sustainability of the deodorizing function, the composite deodorant component (E) obtained by treating the surface of the chemisorption deodorant compound (D) with the iron compound (C) is used. It is important to use.

Next, the iron compound (C) constituting the composite deodorant component (E) used in the deodorant pressure-sensitive adhesive of the present invention will be described. The iron compound (C) is not limited to the type of an aversive odor substance, and its decomposition effect is widely recognized in formaldehyde, ammonia, sulfide, etc. The iron compound (C) includes iron sulfate, iron chloride, iron phosphate. , Iron salts such as iron nitrate, iron oxalate, iron acetate, iron citrate, iron carbonate, iron hydroxide, iron oxide, ammonium iron sulfate, and iron lactate, and complexes such as hexacyanoiron complex and iron dextrin complex .
Among iron salts, compounds containing divalent iron ions are preferred.
Iron ions are divalent and trivalent, and both have a deodorizing effect. However, divalent iron ions form a complex with a nearby odorous substance and reduce the odorous substance to make it non-bromide. It is preferable because of its high effect.
When the copolymer (A) has a carboxyl group, the presence of the carboxyl group and the presence of oxygen or water in the air reduce the odorous substance complexed with the divalent iron ion, Decomposes to release odorless substances and returns to divalent iron ions. Therefore, the deodorizing function of the divalent iron ion is durable.

Examples of those containing divalent iron ions include various iron salts and iron complexes.
As iron salt,
Ferrous sulfate (anhydrous salt, monohydrate, tetrahydrate, pentahydrate, heptahydrate),
Ferrous chloride (anhydrous salt, monohydrate, dihydrate, tetrahydrate, hexahydrate),
Ferrous phosphate (anhydrous salt, monohydrate, 2. pentahydrate, trihydrate, hexahydrate, octahydrate),
Ferrous nitrate (hexahydrate, nine-hydrate),
Ferrous oxalate (anhydrous salt, dihydrate),
Ferrous acetate, ferrous carbonate, ferrous hydroxide, ferrous oxide, ferrous ammonium sulfate, ferrous lactate, etc.
Examples of the complex include a hexacyano iron complex and an iron dextrin complex.
Among the iron salts, ferrous sulfate is preferable, and among the ferrous sulfates, monohydrate, that is, monohydrate is preferable. Anhydrous salts are likely to change to heptahydrate, which is likely to change to basic ferric sulfate. Monohydrate is difficult to absorb moisture, is not easily oxidized, and is highly stable. Monohydrate is also preferred over heptahydrate in that it is easy to disperse.

Next, the chemical adsorption deodorant compound (D) constituting the composite deodorant component (E) used in the deodorant pressure-sensitive adhesive of the present invention will be described.
The chemisorption deodorant compound (D)
A polyamine compound-supported silicon dioxide compound having two or more primary amino groups (hereinafter referred to as “amino group-supported silicon dioxide compound”) (d1),
Zirconium phosphate (d2),
Hydrous zirconium oxide (d3)
And 1 type (s) or 2 or more types can be appropriately selected from the group consisting of the copper compound (d4).
The above-mentioned iron compound (C) decomposes odorous substances and thus has a sustained function, whereas these chemisorption type deodorant compounds (D) have a quick-acting function because they chemisorb odor components.

Of the chemisorption deodorant compound (D), the amino group-supported silicon dioxide compound (d1) is a compound in which a polyamine compound having two or more primary amino groups is supported on the surface of the silicon dioxide compound. .
The polyamine compound is supported by adding a liquid polyamine compound directly to silicon dioxide. Specifically, it can carry | support by the method similar to the surface treatment method of the chemisorption type deodorant compound (D) by an iron compound (C) mentioned later.
Examples of the polyamine compound having two or more primary amino groups include hexamethylenediamine, diethylenetriamine, ethylenediamine, and phenyldiamine.
The amino group-supported silicon dioxide compound (d1) favorably adsorbs aldehyde compounds such as formaldehyde.
Since silicon dioxide itself has a porous surface and a large surface area, it has a deodorizing function. However, the deodorization mechanism without any surface treatment is that the odorous substance is simply taken into the holes, and the odorous substance is detached and diffused when heated.
In contrast, in the amino group-supported silicon dioxide compound (d1), the “—CHO” portion of formaldehyde is modified to “—CH (OH) NH—” by the amino group present on the surface derived from the polyamine compound. Therefore, no odor is emitted even when heated.
The amount of the polyamine compound supported is preferably in the range of 0.01 to 20 parts by weight with respect to 100 parts by weight of silicon dioxide. If it is less than 0.01 part by weight, it is close to the untreated state, so that once adsorbed odorous components are easily desorbed. On the other hand, when the amount is more than 20 parts by weight, the adsorption site of silicon dioxide is blocked by the polyamine compound, so that the adsorptivity of the odor component is lowered, which is not preferable.

Of the chemisorption deodorant compound (D), zirconium phosphate (d2) is particularly effective for deodorizing ammonia and amines.
For example, “—OH” of a phosphate group in zirconium phosphate (d2) reacts with ammonia (NH ₃ ) to form an ionic bond between “NH ₄ ⁺ ” and “—O ⁻ ”, and a deodorizing function To demonstrate.

Of the chemisorption deodorant compound (D), zirconium phosphate (d2) can be used alone, but when used in combination with the copper compound (d4), it is more effective for deodorizing sulfides such as mercaptans and hydrogen sulfide. is there.
Examples of the copper compound (d4) used in the present invention include copper carbonate, copper phosphate, copper hydroxide, and copper sulfate, with copper carbonate being preferred. Copper is useful as a substance having an antibacterial function and a deodorizing function. However, metallic copper lacks stability and tends to rust. Compounds such as copper carbonate and copper phosphate are not easily rusted and have stable antibacterial and deodorant functions.
Copper and zirconium form a coordination bond with a sulfur atom, and are effective in deodorizing sulfides such as hydrogen sulfide and mercaptans. The formation of coordination bonds is faster with copper. Since zirconium is less active than copper, the formation of coordination bonds is slower than copper. The difference in coordination bond formation rate is important for deodorization, and the coexistence of the copper compound (d4) and the zirconium phosphate compound (d2) can provide both immediate effect and sustainability of the deodorization function. .

Hydrogen sulfide may become weak dibasic acid in the presence of water, and it is divided into “2H ⁺ ” and “S ²⁻ ”. In this case, coordination bonds with copper and zirconium are difficult to form. Become. But instead, as shown by the reaction formula below of formula (I), derived from the zirconium phosphate "OH ^-" and copper carbonate, i.e. derived from a "Cu (OH) ₂ CuCO _3" "OH ^- ”And a copper ion are involved in the formation of an ionic bond, exhibiting a deodorizing function.
2H ⁺ + S ² + + 2OH ⁻ + Cu ²⁺ → CuS + 2H ₂ O Formula (I)

When the zirconium phosphate (d2) and the copper compound (d4) are used in combination, (d2) / (d4) = 90 / 10-60 / 40 (weight ratio) is preferable, and 80 / 20-70 / 30 It is more preferable that When the copper compound (d4) is less than 10%, the effect of copper is reduced and the deodorizing effect is lowered. On the other hand, when the amount of the copper compound (d4) exceeds 40%, the activity of copper becomes too large, lacks stability, and causes discoloration and deterioration of adhesive properties.
In addition, when using together zirconium phosphate (d2) and a copper compound (d4), both can be mixed in advance and then mixed into the copolymer (A) or the like. Zirconium phosphate (d2) and copper compound (d4) can also be mixed.
Note that the copper compound (d4) is not necessarily used in combination with zirconium phosphate (d2), and may be used alone.

  Of the chemisorption deodorant compound (D), the hydrous zirconium oxide (d3) is effective for deodorizing acids. Hydrous zirconium oxide (d3) is a hydrate, and “—OH” of the hydrate reacts with “—COOH” of the acid to cause no bromination.

The composite deodorant component (E) used in the present invention can be obtained by using a known method such as a wet process or a dry process.
In the wet treatment, a chemical adsorption deodorant compound (D) and a surface treatment iron compound (C) are added and immersed in a polar solvent such as water or alcohol such as ethanol, and a Henschel mixer, a super mixer, etc. After mixing uniformly using a shearing force mixer, the method of removing the solvent by evaporating and drying, or the one in which the iron compound (C) for surface treatment is dispersed or dissolved in the solvent is a chemisorption deodorant compound There are a method of removing the solvent after spraying (D) and drying, or a method of melting the iron compound (C) for surface treatment into a liquid and mixing it with the chemisorption deodorant compound (D).
In the wet treatment, it is preferable to have a heat drying step during or after the surface treatment since the water content due to moisture adsorption or the like can be greatly reduced.

In the dry treatment, when the chemisorption deodorant compound (D) is pulverized with a fluid energy pulverizer such as a micronizer, jet mill, or steam mill, or a stirrer such as a super mixer or a Henschel mixer, iron for surface treatment is used. Compound (C) is added. Usually, compressed air, heated compressed air, steam or the like is used as the fluid in the fluid energy pulverizer. When a solid compound is added as it is, a surface fusion (mechano-fusion) effect can be expected by shearing heat generation.
Moreover, the polyhydric alcohol solution which melt | dissolved the solid compound in the solvent can also be used for the said process process. For example, an ethanol solution of trimethylolethane, a water ethanol (1: 1) solution, or the like can be given.
Since the surface treatment compound obtained by physical treatment such as chemical treatment or mechanofusion by wet treatment or dry treatment in this way, the treatment agent is difficult to peel off even when subjected to mechanical shearing force such as subsequent dispersion treatment, preferable.

The composite deodorant component (E) is preferably one obtained by surface-treating 0.5 to 5 parts by weight of the chemisorption deodorant compound (D) with 1 part by weight of the iron compound (C). 1 to 3 parts by weight of the chemisorption deodorant compound (D) is more preferable.
When the iron compound (C) is relatively increased, the immediate effect of the deodorizing function is likely to be impaired. On the other hand, when the iron compound (C) is relatively decreased, the durability of the deodorizing function is easily impaired.

When blending the composite deodorant component (E) into the copolymer (A) solution, the composite deodorant component (E) may be dispersed using a dispersing machine such as ball mill dispersion or bead mill dispersion. preferable. The average particle size after dispersion is preferably 5 μm or less in consideration of the thickness of the pressure-sensitive adhesive layer and the finished appearance.
The composite deodorant component (E) is 1 to 30 parts by weight of the iron compound (C) and 1 to 50 parts by weight of the chemisorption deodorant compound (D) with respect to 100 parts by weight of the copolymer (A). The iron compound (C) is preferably contained so as to be 1 to 20 parts by weight, and more preferably 1 to 10 parts by weight. The chemisorption deodorant compound (D) is preferably contained in an amount of 1 to 25 parts by weight, and more preferably 2 to 10 parts by weight.
When the amount of the iron compound (C) and the chemisorption deodorant compound (D) is too small, the deodorizing effect tends to be reduced. On the other hand, if the amount of both components is excessive, the deodorizing effect is enhanced, but a large amount is present in the pressure-sensitive adhesive layer of the pressure-sensitive adhesive processed product, and the cohesive force of the pressure-sensitive adhesive layer is likely to be insufficient.

The deodorant pressure-sensitive adhesive of the present invention preferably further contains a tackifier resin (F) in order to maintain and improve the pressure-sensitive adhesive properties. About the kind etc., a well-known thing can be used.
For example, rosin-based and petroleum resin-based ones can be mentioned. Examples of rosin-based include polymerized rosin, heterogeneous rosin, hydrogenated rosin, polymerized rosin and other rosin esters, and petroleum resin-based terpene-based. And synthetic resins such as polyphenolic resins, styrene-based resins, and the like.
When the tackifying resin is used, the weight ratio of the copolymer (A) and the tackifying resin (F) is preferably (A) / (F) = 90 / 10-60 / 40, and 80 / 20-70. / 30 is more preferable. If the tackifying resin (F) is less than 10%, it is difficult to sufficiently obtain the effect of improving the adhesive force. On the other hand, when there are more tackifying resin (F) than 40%, an adhesive layer will become hard easily.

  Furthermore, the deodorant pressure-sensitive adhesive of the present invention includes fillers, pigments, dyes, diluents, anti-aging agents, polymerization inhibitors, UV absorbers, UV stabilizers and the like blended in known pressure-sensitive adhesive compositions. Various additives may be included as necessary. Only one kind of these additives may be used, or two or more kinds may be appropriately used. Moreover, the addition amount of an additive should just be taken as the quantity from which the desired physical property is obtained, and is not specifically limited.

Various deodorant pressure-sensitive adhesive processed products can be obtained using the deodorant pressure-sensitive adhesive of the present invention.
For example, by applying the deodorant pressure-sensitive adhesive of the present invention to at least one surface of various base materials, drying and providing a deodorant pressure-sensitive adhesive layer, various deodorant pressure-sensitive adhesive processed products are obtained. be able to.
As the base material used, polyethylene, polypropylene, polyester, polystyrene, polyethylene terephthalate (PET), polyvinyl chloride, polycarbonate, cellophane and other plastics; fine paper, kraft paper, crepe paper, glassine paper and the like; woven fabric, Examples of the material include, but are not limited to, a non-woven fabric and the like. Examples of the shape of the substrate include a film shape, a sheet shape, a tape shape, and a plate shape, but are not particularly limited. Moreover, when a base material is a plastic, a foam may be sufficient.

The method for forming the pressure-sensitive adhesive layer on the substrate using the deodorant pressure-sensitive adhesive of the present invention, that is, the method for producing the pressure-sensitive adhesive product is not particularly limited, and various known methods should be adopted. Can do. As the method, for example, a method in which an adhesive is directly applied to a substrate and dried; an adhesive is applied to a release paper and dried to form an adhesive layer, and then the adhesive layer and the substrate are bonded together And a method of transferring the pressure-sensitive adhesive layer to the substrate.
As a device for applying the deodorant pressure-sensitive adhesive of the present invention to a substrate or release paper, a conventionally known coating device can be used.
Further, the drying temperature is not particularly limited, but the solvent in the pressure-sensitive adhesive volatilizes, and the hydroxyl group and / or carboxyl group in the copolymer (A) contained in the pressure-sensitive adhesive, and these Any temperature can be used as long as it can react with the curing agent (B) that can react.
In some applications, the adhesive may be applied directly to the adherend. Also, after the pressure-sensitive adhesive is applied to the release paper and dried, the coated product is peeled from the release paper, whereby the pressure-sensitive adhesive layer itself is formed into a film shape, a sheet shape, a tape shape, a plate shape, or the like. An adhesive processed product can also be manufactured.

  EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but these do not limit the scope of the present invention. In the examples, “part” is “part by weight”, and “%” is “% by weight”.

[Example 1]
Using a polymerization apparatus equipped with a stirrer, a thermometer, a dropping funnel, and a refluxer, 64.9 parts of n-butyl acrylate, 25 parts of 2-ethylhexyl acrylate, 7 parts of ethyl acrylate, 3 parts of acrylic acid, 2-hydroxyethyl acrylate 0.1 part, 120 parts of ethyl acetate, 0.85 part of α-pinene, and 0.03 part of benzoyl peroxide were copolymerized under reflux for 2 hours, and after 1 hour and 2 hours while maintaining the reaction temperature. 0.023 parts of benzoyl oxide was added. After the addition, the reaction was allowed to proceed for 2 hours, and then 0.022 parts of t-butyl-oxy-2-ethylhexanoate was added after 1 hour, 2 hours, and 3 hours. After the last addition, the reaction was further allowed to proceed for 2 hours, and after cooling, diluted with ethyl acetate, when the liquid temperature became 60 ° C. or less, 0.1 part of hydroquinone derivative (“Nonflex Albert” manufactured by Seiko Chemical Co., Ltd.) was added, After sufficiently stirring, the copolymer solution was taken out. The weight average molecular weight of the copolymer in terms of polystyrene as determined by gel permeation chromatography (hereinafter referred to as “GPC”) is about 650,000, the solid content of the copolymer solution is 45%, and the viscosity Was 25000 mPa · s.
The glass transition temperature (calculated value) of the copolymer is -45 ° C.
To 36 parts of the obtained copolymer solution, 9 parts of tackifying resin and ethyl acetate are added, the solid content is 45%, the viscosity is 8000 mPa · s, and 0.1 part of acetylacetone is added and blended therein. The main agent was obtained.
In addition, the measurement of the non volatile matter was calculated | required from the weight ratio before and behind drying after 150 degreeC-20 minutes with an electric oven. The viscosity is a value measured with a B-type viscometer (# 3 rotor, 12 rpm) at 25 ° C.

Silicon dioxide (particle size: 1 μm) was added to a Henschel mixer and stirred, and phenyldiamine was added so as to cover the surface layer at a ratio of 5.0 parts with respect to 100 parts of silicon dioxide, followed by stirring for about 5 to 10 minutes. Thereafter, it was taken out to obtain an amino group-supported silicon dioxide compound (d1-1) coated with phenyldiamine.
100 parts by weight of ferrous sulfate monohydrate was added to 150 parts by weight of the resulting amino group-supported silicon dioxide compound (d1-1), mixed and stirred for 1 hour at 25 ° C. with a super mixer, and then steamed. A dry deodorization component (E1) surface-treated with ferrous sulfate monohydrate was obtained by dry treatment in a mill.

2.5 parts of the obtained composite deodorant component (E1) is added to 100 parts by weight of the main component solid content of the pressure-sensitive adhesive, and dispersed with a bead mill disperser. The average of the composite deodorant component (E1) The particle size was 4.5 μm.
Next, 5.5 parts by weight of an ethyl acetate solution (solid content: 37.5%) of a trimethylolpropane adduct of toluene diisocyanate as a curing agent is blended with 100 parts by weight of the main component of the pressure-sensitive adhesive as a curing agent. An adhesive was obtained. Various evaluations were made according to the methods described below.

[Example 2]
A composite deodorant component (E2) was obtained in the same manner as in Example 1 except that the amount of the amino group-supported silicon dioxide compound (d1-1) was 250 parts by weight, and further to the composite deodorant component (E1). Instead, a deodorant pressure-sensitive adhesive was obtained in the same manner as in Example 1 except that 3.5 parts of the composite deodorant component (E2) was used.

[Example 3]
A composite deodorant component (E3) was obtained in the same manner as in Example 1 except that zirconium phosphate was used instead of the amino group-supported silicon dioxide compound (d1-1). An agent was obtained.

[Example 4]
A composite deodorant component (E4) was obtained in the same manner as in Example 1 except that hydrous zirconium oxide was used instead of the amino group-supported silicon dioxide compound (d1-1). An agent was obtained.

[Example 5]
The same as in Example 1 except that 150 parts by weight of a mixture containing zirconium phosphate and copper carbonate in a ratio of 76/24 (weight ratio) was used instead of the amino group-supported silicon dioxide compound (d1-1). A composite deodorant component (E5) was obtained, and a deodorant pressure-sensitive adhesive was obtained in the same manner.
The obtained deodorant pressure-sensitive adhesive was 1.14 parts by weight of zirconium phosphate, 0.36 parts by weight of copper carbonate, ferrous sulfate / monohydrate with respect to 100 parts by weight of the main component solid content of the pressure-sensitive adhesive. 1 part by weight of the product is included.

[Example 6]
Instead of the amino group-supported silicon dioxide compound (d1-1), 75 parts by weight of a mixture containing zirconium phosphate and copper carbonate in a ratio of 76/24 (weight ratio) and 75 parts by weight of zirconium phosphate were used. Except for the above, the composite deodorant component (E6) was obtained in the same manner as in Example 1, and the deodorant adhesive was obtained in the same manner as in Example 1 except that 2.5 parts of the composite deodorant component (E6) was used. An agent was obtained.
The obtained deodorant pressure-sensitive adhesive was 1.32 parts by weight of zirconium phosphate, 0.18 parts by weight of copper carbonate, ferrous sulfate / monohydrate with respect to 100 parts by weight of the main component solid content of the pressure-sensitive adhesive. 1 part by weight of the product is included.

[Example 7]
A composite deodorant component (E7) was obtained in the same manner as in Example 1 except that 100 parts by weight of ferrous sulfate / anhydrous salt was used instead of ferrous sulfate / monohydrate. A deodorant pressure-sensitive adhesive was obtained.

[Example 8]
Composite deodorant component (E8) in the same manner as in Example 1 except that 200 parts by weight of the amino group-supported silicon dioxide compound (d1-1) and 50 parts by weight of ferrous sulfate monohydrate were used. In the same manner, a deodorant pressure-sensitive adhesive was obtained.

[Example 9]
The composite deodorant component (E9) was prepared in the same manner as in Example 1 except that 150 parts by weight of the amino group-supported silicon dioxide compound (d1-1) and 4000 parts by weight of ferrous sulfate monohydrate were used. A deodorant pressure-sensitive adhesive was obtained in the same manner as in Example 1 except that 41.5 parts of the composite deodorant component (E9) was used.

[Example 10]
The composite deodorant component (E10) was prepared in the same manner as in Example 1 except that 50 parts by weight of the amino group-supported silicon dioxide compound (d1-1) and 200 parts by weight of ferrous sulfate monohydrate were used. A deodorant pressure-sensitive adhesive was obtained in the same manner as in Example 1 except that 2.5 parts of the composite deodorant component (E10) was used.

[Example 11]
The composite deodorant component (E11) was prepared in the same manner as in Example 1 except that the amino group-supported silicon dioxide compound (d1-1) was 4000 parts by weight and the ferrous sulfate monohydrate was 100 parts by weight. A deodorant pressure-sensitive adhesive was obtained in the same manner as in Example 1 except that 41 parts of the composite deodorant component (E11) was used.

[Comparative Examples 1-4]
A pressure-sensitive adhesive was obtained in the same manner as in Example 1 except that the composite deodorant component (E) was not used.

[Comparative Example 5]
A deodorant pressure-sensitive adhesive was obtained in the same manner as in Example 1 except that 2.5 parts by weight of the amino group-supported silicon dioxide compound (d1-1) was used instead of the composite deodorant component (E1).

[Comparative Example 6]
A deodorant pressure-sensitive adhesive was obtained in the same manner as in Example 1 except that 2.5 parts by weight of zirconium phosphate was used instead of the composite deodorant component (E1).

[Comparative Example 7]
A deodorant pressure-sensitive adhesive was obtained in the same manner as in Example 1 except that 2.5 parts by weight of hydrous zirconium oxide was used instead of the composite deodorant component (E1).

[Comparative Example 8]
Example 1 was used except that 2.5 parts by weight of a mixture containing zirconium phosphate and copper carbonate in a ratio of 76/24 (weight ratio) was used instead of the composite deodorant component (E1). A deodorant pressure-sensitive adhesive was obtained.

[Comparative Example 9]
A deodorant pressure-sensitive adhesive was obtained in the same manner as in Example 1 except that 2.5 parts by weight of ferrous sulfate monohydrate was used instead of the composite deodorant component (E1).

<Evaluation>
(1) Preparation of test coated material A test coated material for evaluating the pressure-sensitive adhesive obtained in each Example and each Comparative Example was prepared by the following method.
That is, an adhesive was applied to a commercially available release paper with an applicator. Thereafter, it was put in an oven at 100 ° C. and dried for 2 minutes. A polyethylene terephthalate (PET) film having a thickness of 50 μm was layered on the surface of the formed pressure-sensitive adhesive layer, and pressure-bonded with a rubber roll and bonded. The produced coated material was placed in an oven at 40 ° C. for 3 days to be cured, and a test coated material having a pressure-sensitive adhesive layer thickness of 20 μm was obtained.

(2) Confirmation of deodorizing effect Peel off the release paper from the coated product obtained in (1) above, paste it on the nonwoven fabric to the exposed adhesive layer, cut it to 10 x 10 cm, and remove the deodorizing test piece. Produced.
Next, so that the gas concentration is 20 ppm in the 3 L bag for immediate effect evaluation, and the gas concentration is 50 ppm in the 3 L bag for sustainability evaluation,
Formaldehyde (Examples 1, 2, 7-11, Comparative Examples 1, 5, 9)
Ammonia (Example 3, Comparative Examples 2 and 6),
Trimethylamine (Example 3, Comparative Examples 2 and 6),
An aqueous solution of acetic acid (Example 4, Comparative Examples 3, 7),
Benzene solution of methyl mercaptan (Examples 5 and 6, Comparative Examples 4 and 8)
Hydrogen sulfide (Examples 5 and 6 and Comparative Examples 4 and 8)
Were injected respectively. Except hydrogen sulfide, in order to volatilize each odorous substance sufficiently in the bag, it was left in a thermostatic chamber at 23 ° C. for 60 minutes.

Insert the above 10cm x 10cm deodorization test pieces into each bag, measure the initial concentration using a detector tube and a sampling device, and in the case of immediate effect evaluation, after 6 hours, every hour, then The odor in the bag was evaluated by reading the scale on the detector tube every 2 hours until 14 hours and after 24 hours after 14 hours.
On the other hand, in the case of sustainability evaluation, the initial concentration and the concentration after one week were measured in the same manner (first time), and the test piece was taken out. Next, the test piece taken out from the first bag is put in a newly prepared bag (second bag) so that the gas concentration becomes 50 ppm, and the concentration after one week is measured (second time). The piece was removed. Similarly, a third bag was prepared, a test piece taken out from the second bag was put in, the concentration after one week was measured (third time), and the test piece was taken out. Similarly, a fourth bag was prepared, a test piece taken out from the third bag was put, and the concentration after one week was measured (fourth time).

(3) Adhesive strength measurement The test coating obtained in the above (1) was cut into 25 mm × 100 mm, the release paper was peeled off, attached to a stainless steel plate as an adherend, and then crimped with a 2 kg roll. Immediately after pasting (initial adhesive force) and 24 hours after pasting (permanent adhesive force) at 180 ° peel in an environment of 23 ° C.-50% RH, the adhesive strength (mN / 25 mm) was obtained.

(4) Holding power test The test coating obtained in (1) above is cut to 25 mm x 100 mm, the release paper is peeled off, and a 25 mm x 25 mm square is applied to the end of the adherend stainless steel plate, and then a 2 kg roll. After pressure bonding, a 1 kg load was applied to the coated material and left in an environment of 40 ° C. The displacement (mm) of the sticking position after 70,000 seconds or the time (second) until dropping was obtained.

(5) Ball tack The release paper was peeled off from the test coated product obtained in (1), and a ball tack test was performed in a 23 ° C.-50% RH environment according to JIS Z0237.

  The above evaluation results are shown in Tables 1-4.

With the deodorant pressure-sensitive adhesive of the present invention, it is possible to obtain a pressure-sensitive adhesive product having good pressure-sensitive adhesive properties and excellent deodorizing function immediate effect and sustainability. The deodorant pressure-sensitive adhesive of the present invention is used for vehicle interiors, hospitals, residences, and the like and can be suitably used for wallpaper and foam sheets, and can greatly contribute to environmental improvement.

Claims (9)

A copolymer having a hydroxyl group and / or a carboxyl group (A), a hydroxyl group and / or a carboxyl obtained by radical polymerization of a radical polymerizable unsaturated monomer capable of forming a copolymer having a glass transition temperature of -80 to -10 ° C. A deodorant pressure-sensitive adhesive containing a curing agent (B) having a functional group capable of reacting with a group and a composite deodorant component (E) and not containing toluene or xylene,
The composite deodorant component (E) is a polyamine compound-supported silicon dioxide compound (d1) having two or more primary amino groups, zirconium phosphate (d2), hydrous zirconium oxide (d3), and copper compound (d4) A deodorant pressure-sensitive adhesive, wherein the surface of at least one or more chemisorption deodorant compounds (D) selected from the group consisting of is treated with an iron compound (C). The deodorant pressure-sensitive adhesive according to claim 1, further comprising an organic solvent other than toluene and xylene. The deodorant pressure-sensitive adhesive according to claim 1 or 2, wherein the iron compound (C) is a compound containing a divalent iron ion. The composite deodorant component (E) is obtained by surface-treating 0.5 to 5 parts by weight of a chemisorption deodorant compound (D) with 1 part by weight of an iron compound (C). Item 4. The deodorant pressure-sensitive adhesive according to any one of Items 1 to 3. The deodorant pressure-sensitive adhesive according to any one of claims 1 to 4, wherein the copper compound (d4) is any one of copper carbonate, copper phosphate and copper hydroxide. The iron compound (C) is contained in an amount of 1 to 30 parts by weight and the chemisorption deodorant compound (D) is contained in an amount of 1 to 50 parts by weight with respect to 100 parts by weight of the copolymer (A). Thru | or 5 deodorizing adhesive. The deodorant pressure-sensitive adhesive according to any one of claims 1 to 6, further comprising a tackifier resin (F). The deodorant pressure-sensitive adhesive according to claim 7, wherein the weight ratio of the copolymer (A) to the tackifier resin (F) is (A) / (F) = 90/10 to 60/40. . A deodorant pressure-sensitive adhesive processed product comprising a deodorant pressure-sensitive adhesive layer formed from the deodorant pressure-sensitive adhesive according to any one of claims 1 to 8 on a substrate.