JPWO2011111534A1 - Flame retardant adhesive composition, flame retardant adhesive tape, and flame retardant adhesive sheet - Google Patents

Abstract

A flame retardant pressure-sensitive adhesive composition excellent in flame retardancy and also excellent in initial tackiness and stability with time, and a flame retardant pressure-sensitive adhesive tape using such a flame retardant pressure-sensitive adhesive composition and A flame-retardant pressure-sensitive adhesive sheet is provided. A flame retardant pressure-sensitive adhesive composition containing a (meth) acrylic acid ester copolymer as a component (A) and a flame retardant as a component (B), and the flame retardant as a component (B) The amount of the component (B) is set to a value within the range of 70 to 200 parts by weight with respect to 100 parts by weight of the component (A), and the component (A) As monomer components for polymerization, the following components (a) to (c) are included. (A) C1-C12 (meth) acrylic acid alkyl ester: 100 parts by weight (b) Carboxyl group-containing vinyl compound: 0 part by weight or 0-1 part by weight (however, 0 part by weight is not included) ( c) Nitrogen-containing vinyl compound: 1 to 70 parts by weight

Description

  The present invention relates to a flame-retardant pressure-sensitive adhesive composition, a flame-retardant pressure-sensitive adhesive tape, and a flame-retardant pressure-sensitive adhesive sheet. In particular, the present invention relates to a flame retardant pressure-sensitive adhesive composition, a flame retardant pressure-sensitive adhesive tape, and a flame retardant pressure-sensitive adhesive sheet that are excellent in flame retardancy and also excellent in initial tackiness and adhesive temporal stability.

2. Description of the Related Art Conventionally, an electrical insulating tape or the like used for an electronic component or the like is required to have a high flame retardance of, for example, VTM-0 to 2 level in the UL94 standard as a flame retardance standard.
Therefore, in order to improve the flame retardancy of the pressure-sensitive adhesive composition in an electrical insulating tape or the like, generally, a method of incorporating various flame retardants into the pressure-sensitive adhesive composition has been adopted. Such flame retardants are generally halogen compounds such as chlorine and bromine, and those using a halogen compound and antimony oxide in combination.
However, halogen-based flame retardants are not only harmful to the human body due to the generation of halogen-based gases during combustion, but are also colored, so they are difficult to use for electrical insulating tapes that require transparency. It was observed.

In order to solve these problems, a method using a phosphate ester flame retardant as a flame retardant other than a halogen compound has been proposed.
That is, a flame-retardant pressure-sensitive adhesive tape in which a pressure-sensitive adhesive layer containing a phosphate ester-based flame retardant (α) and a melamine-based resin particle (β) is provided on at least one surface of a substrate, The total blending amount represented by (α + β) is 45 to 250 parts by weight with respect to 100 parts by weight of the base polymer, and the ratio represented by (α / β) is in the range of 0.2 to 5 A flame retardant pressure-sensitive adhesive tape in which a phosphate ester flame retardant (α) and melamine resin particles (β) are blended so as to have a value is disclosed (for example, see Patent Document 1).

  Further, a flame-retardant adhesive tape provided with an adhesive layer comprising an aromatic condensed phosphate ester flame retardant (α) and a phosphate ester (β) on at least one surface of a substrate, The total blending amount represented by (α + β) is 45 to 250 parts by weight with respect to 100 parts by weight of the base polymer in the pressure-sensitive adhesive layer, and the ratio represented by (α / β) is 0.3 to 3 A flame retardant pressure-sensitive adhesive tape comprising an aromatic condensed phosphate ester flame retardant (α) and a phosphate ester (β) is disclosed so as to have a value within the range (for example, Patent Document 2). reference).

Japanese Patent No. 3983889 (Claims) Japanese Patent No. 3984890 (Claims)

However, in the flame-retardant adhesive tape using the phosphoric ester-based flame retardant disclosed in Patent Documents 1 and 2, it is not easy to achieve a good balance between flame retardancy and adhesiveness, which are reciprocal characteristics. There was a problem.
That is, when a predetermined amount of a carboxyl group-containing vinyl compound is used in order to improve adhesiveness, the adhesive main agent becomes an acid-based adhesive main agent, and the acid-based adhesive main agent serves as a catalyst to form a phosphate ester-based flame retardant. As a result, there was a problem that the adhesiveness was remarkably lowered with time.

Therefore, the present inventors made extensive efforts in view of the above circumstances, and as a monomer component when copolymerizing the (meth) acrylic acid ester copolymer as an adhesive main agent, (b) While strictly limiting the compounding amount of the carboxyl group-containing vinyl compound, (c) while using a predetermined amount of the nitrogen-containing vinyl compound, a predetermined amount of aromatic phosphate ester as a flame retardant with respect to the obtained adhesive main agent By using it, it is possible to effectively improve the initial adhesiveness while effectively suppressing the hydrolysis of the phosphate ester in the adhesive composition, and also effective in reducing the adhesiveness over time. The present invention has been completed by finding that it can be reduced.
That is, an object of the present invention is to provide a flame-retardant pressure-sensitive adhesive composition that is excellent in flame retardancy and also excellent in initial tackiness and adhesive temporal stability, and such a flame-retardant pressure-sensitive adhesive composition. It is providing the flame-retardant adhesive tape and flame-retardant adhesive sheet using this.

According to the present invention, a flame retardant pressure-sensitive adhesive composition comprising a (meth) acrylic acid ester copolymer as the component (A) and a flame retardant as the component (B), wherein the component (B) A certain flame retardant contains an aromatic phosphate, and the blending amount of the flame retardant as the component (B) is 70 parts by weight with respect to 100 parts by weight of the (meth) acrylic acid ester copolymer as the component (A). As a monomer component when copolymerizing the (meth) acrylic acid ester copolymer that is the component (A) with a value within the range of ~ 200 parts by weight, the following monomer components (a) to ( The flame-retardant pressure-sensitive adhesive composition characterized by containing c) is provided, and the above-described problems can be solved.
(A) (meth) acrylic acid ester having 1 to 12 carbon atoms of alkyl group: 100 parts by weight (b) carboxyl group-containing vinyl compound: 0 part by weight or 0 to 1 part by weight (however, 0 part by weight is not included) .)
(C) Nitrogen-containing vinyl compound: 1 to 70 parts by weight That is, in the case of the flame retardant pressure-sensitive adhesive composition of the present invention, flame retardant is obtained by containing an aromatic phosphate ester as a flame retardant in a predetermined ratio. While maintaining the safety and transparency of the pressure-sensitive adhesive composition, excellent flame retardancy can be obtained.
In addition, as the component (b), a carboxyl group-containing vinyl compound, that is, a vinyl compound having a carboxyl group in the molecule is strictly limited to a predetermined amount or less, and more preferably, it is substantially not used. Due to the catalytic action of the group, the aromatic phosphate ester as a flame retardant hydrolyzes, and as a result, the flame retardancy and tackiness of the flame retardant adhesive composition are reduced over time. Can be suppressed.
Furthermore, since a predetermined amount of a nitrogen-containing vinyl compound, that is, a vinyl compound having a nitrogen atom in the molecule is used as the component (c), good adhesive properties at the initial stage and over time can be obtained.
More specifically, it is considered that the initial tackiness in the flame-retardant pressure-sensitive adhesive composition is usually insufficient by strictly limiting the blending amount of the carboxyl group-containing vinyl compound as the component (b) to a predetermined value or less. However, since a predetermined amount of the nitrogen-containing vinyl compound as component (c) is used, sufficient initial adhesiveness can be obtained, and such adhesiveness can be effectively maintained over time. can do.
In addition, the “flame retardant pressure-sensitive adhesive composition” in the present invention is an uncrosslinked flame retardant pressure-sensitive adhesive composition or a cross-linked flame retardant pressure-sensitive adhesive composition. If it is a flame retardant pressure-sensitive adhesive composition having a composition, it means a broad meaning.

In constituting the flame-retardant pressure-sensitive adhesive composition of the present invention, the nitrogen-containing vinyl compound as component (c) is preferably a vinyl compound having an amide structure in the molecule.
By comprising in this way, the adhesiveness of a flame-retardant adhesive composition can be improved more effectively, suppressing the hydrolysis of aromatic phosphate ester more stably.

In constituting the flame-retardant pressure-sensitive adhesive composition of the present invention, the vinyl compound having an amide structure in the molecule as the component (c) is preferably a (meth) acrylamide derivative.
By comprising in this way, the adhesiveness of a flame-retardant adhesive composition can be improved more effectively, suppressing the hydrolysis of aromatic phosphate ester more stably.

Moreover, in constituting the flame retardant pressure-sensitive adhesive composition of the present invention, at least one of the aromatic phosphate esters is a liquid aromatic phosphate ester, and the blending amount of the liquid aromatic phosphate ester is as follows: It is preferable to set it as the value of 30 weight% or more with respect to the whole quantity of the flame retardant which is (B) component.
By using a predetermined amount of the liquid aromatic phosphate ester in this way, it is possible to effectively prevent the phenomenon that the flame retardant precipitates on the surface of the flame retardant pressure-sensitive adhesive composition, that is, the so-called blooming, while maintaining the flame retardancy. Can be suppressed.
Further, by using a predetermined amount of such a liquid aromatic phosphate ester, (meth) acrylic acid which is component (A) containing (c) component aromatic ring-containing vinyl compound such as acryloylmorpholine as a structural unit An excellent plasticizing effect can be exerted on the ester copolymer, and the adhesive property in the flame retardant adhesive composition can be further improved.

In constituting the flame-retardant pressure-sensitive adhesive composition of the present invention, the above-mentioned liquid aromatic phosphate is preferably a condensed liquid aromatic phosphate.
By comprising in this way, generation | occurrence | production of blooming can be suppressed effectively and higher flame retardance can be obtained compared with the case where a non-condensation type liquid aromatic phosphate ester is added. .
Further, by using such a condensed liquid aromatic phosphate ester, (meth) acrylic acid as component (A) containing (c) component nitrogen-containing vinyl compound such as acryloylmorpholine as a structural unit An excellent plasticizing effect can be exerted on the ester copolymer, and the adhesive property in the flame retardant adhesive composition can be further improved.

In constituting the flame-retardant pressure-sensitive adhesive composition of the present invention, the nitrogen-containing vinyl compound (c) is acryloylmorpholine, and the flame retardant (B) is 1,3- Preferably, it is at least one of phenylene bis (dixylenyl phosphate), bisphenol A bis (diphenyl phosphate) and 1,3-phenylene bis (diphenyl phosphate).
By comprising in this way, the flame retardant which is (B) component with respect to the (meth) acrylic acid ester copolymer which is (A) component derived from the predetermined | prescribed monomer component has a predetermined plastic effect. And exhibit good adhesive properties in the flame retardant adhesive composition.
Moreover, if it is such a flame retardant, generation | occurrence | production of blooming from the (meth) acrylic acid ester copolymer which is (A) component can be suppressed effectively, and higher flame retardance will be acquired. Can do.

Further, in constituting the flame retardant pressure-sensitive adhesive composition of the present invention, as a further monomer component (d) when copolymerizing the (meth) acrylic acid ester copolymer as the component (A), a hydroxyl group-containing The vinyl compound, that is, the vinyl compound having a hydroxyl group (hydroxyl group) in the molecule is preferably blended at a value in the range of 1 to 15 parts by weight with respect to 100 parts by weight of the monomer component (a).
By comprising in this way, when a crosslinking agent is added to a flame-retardant adhesive composition, (meth) acrylic acid ester copolymer can be bridge | crosslinked effectively and flame-retardant adhesion The adhesive strength and storage elastic modulus of the agent composition can be easily adjusted.

Moreover, in comprising the flame-retardant adhesive composition of this invention, it is preferable to contain the crosslinking agent with respect to the (meth) acrylic acid ester copolymer which is (A) component as (C) component.
By comprising in this way, adjustment of the adhesive force and storage elastic modulus of a flame-retardant adhesive composition can be performed easily.

Another aspect of the present invention is a flame retardancy comprising (meth) acrylic acid ester copolymer as component (A) and flame retardant as component (B) on one or both sides of the substrate. A flame-retardant pressure-sensitive adhesive tape comprising the pressure-sensitive adhesive composition as a pressure-sensitive adhesive layer, wherein the flame retardant as the component (B) contains an aromatic phosphate and the amount of the flame retardant as the component (B) Is a value within the range of 70 to 200 parts by weight with respect to 100 parts by weight of the (meth) acrylic acid ester copolymer as the component (A), and the (meth) acrylic acid ester as the component (A) A flame retardant pressure-sensitive adhesive tape comprising the following components (a) to (c) as monomer components for copolymerizing a copolymer.
(A) (meth) acrylic acid alkyl ester having 1 to 12 carbon atoms of alkyl group: 100 parts by weight (b) carboxyl group-containing vinyl compound: 0 part by weight or 0 to 1 part by weight (provided that 0 part by weight is included) Absent.)
(C) Nitrogen-containing vinyl compound: 1 to 70 parts by weight In other words, a flame-retardant adhesive tape not only having excellent adhesiveness but also satisfying a predetermined level of UL94 standard is obtained. In addition, it can be suitably used for applications such as tape for fixing and binding in electronic equipment.

Still another aspect of the present invention is a flame retardant comprising a (meth) acrylic acid ester copolymer as the component (A) and a flame retardant as the component (B) on one or both sides of the substrate. A flame-retardant pressure-sensitive adhesive sheet comprising a pressure-sensitive adhesive composition as a pressure-sensitive adhesive layer, wherein the flame retardant as the component (B) contains an aromatic phosphate ester and the flame retardant as the component (B) The amount is set to a value in the range of 70 to 200 parts by weight with respect to 100 parts by weight of the (meth) acrylic acid ester copolymer as the component (A), and (meth) acrylic acid as the component (A) A flame retardant pressure-sensitive adhesive sheet comprising the following components (a) to (c) as monomer components for copolymerizing an ester copolymer.
(A) (meth) acrylic acid alkyl ester having 1 to 12 carbon atoms of alkyl group: 100 parts by weight (b) carboxyl group-containing vinyl compound: 0 part by weight or 0 to 1 part by weight (provided that 0 part by weight is included) Absent.)
(C) Nitrogen-containing vinyl compound: 1 to 70 parts by weight That is, since a flame-retardant pressure-sensitive adhesive sheet not only having excellent adhesiveness but also satisfying a predetermined level of UL94 standard is obtained, for example, quality indication of flameproofing articles It can be effectively used for applications such as labels, wallpaper, information display labels for electronic equipment casings or parts.

Fig.1 (a)-(d) is the schematic provided in order to demonstrate the usage methods, such as a flame-retardant adhesive composition, and manufacturing methods, such as a flame-retardant adhesive tape. FIG. 2 is a diagram provided for explaining the relationship between the blending ratio of the monomer component (b) and the tackiness of the flame retardant pressure-sensitive adhesive composition. FIG. 3 is a diagram provided for explaining the relationship between the blending ratio of the monomer component (c) and the tackiness of the flame retardant pressure-sensitive adhesive composition. FIG. 4 is a diagram for explaining the function of the liquid aromatic phosphate ester as a plasticizer.

[First Embodiment]
1st Embodiment of this invention is a flame retardant adhesive composition containing the (meth) acrylic acid ester copolymer as (A) component, and the flame retardant as (B) component, The flame retardant as the component (B) contains an aromatic phosphate ester, and the amount of the flame retardant as the component (B) is 100 parts by weight of the (meth) acrylic acid ester copolymer as the component (A). As a monomer component when copolymerizing the (meth) acrylic acid ester copolymer as the component (A) with a value within the range of 70 to 200 parts by weight, the following (a) to (C) It is a flame-retardant adhesive composition characterized by including a component.
(A) (meth) acrylic acid alkyl ester having 1 to 12 carbon atoms of alkyl group: 100 parts by weight (b) carboxyl group-containing vinyl compound: 0 part by weight or 0 to 1 part by weight (provided that 0 part by weight is included) Absent.)
(C) Nitrogen-containing vinyl compound: 1 to 70 parts by weight That is, the first embodiment of the present invention is a flame retardant pressure-sensitive adhesive composition used in the mode illustrated in FIGS. Now, a specific description will be given with reference to the drawings as appropriate.

1. (A) component: (meth) acrylic acid ester copolymer (1) monomer component (1) -1 monomer component (a)
The (meth) acrylic acid ester copolymer that is the component (A) contains a (meth) acrylic acid ester having 1 to 12 carbon atoms in the alkyl group as the monomer component (a) when polymerizing the copolymer. It is characterized by that.
The reason for this is that when the number of carbon atoms of the alkyl group is larger than 12, the stickiness of the obtained flame-retardant pressure-sensitive adhesive composition may decrease due to the orientation and crystallization of the side chains. It is.
On the other hand, when the carbon number of the alkyl group is too small, the storage elastic modulus of the obtained flame-retardant pressure-sensitive adhesive composition becomes too large, and the durability may be insufficient.
Therefore, the carbon number of the alkyl group in the (meth) acrylic acid ester copolymer is more preferably set to a value within the range of 2 to 10, and further preferably set to a value within the range of 3 to 8.

Moreover, as (meth) acrylic acid ester whose carbon number of an alkyl group is the value within the range of 1-12, (meth) acrylic acid methyl, (meth) acrylic acid ethyl, (meth) acrylic acid propyl, ) Butyl acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, ( A single type of decyl (meth) acrylate and dodecyl (meth) acrylate or a combination of two or more types may be mentioned.
Moreover, since the (meth) acrylic acid ester which is the monomer component (a) is a main component constituting the (meth) acrylic acid ester copolymer which is the (A) component, such (meth) acrylic acid The amount of the ester is usually preferably 60% by weight or more of the total monomer components constituting the component (A), more preferably 70 to 99% by weight, More preferably, the value is within the range of 75 to 95% by weight.

(1) -2 Monomer component (b)
In addition, the monomer component (b) when copolymerizing the (meth) acrylic acid ester copolymer as the component (A) is substantially free of a carboxyl group-containing vinyl compound.
More specifically, the blending ratio of the monomer component (b) when the (meth) acrylic acid ester copolymer as the component (A) is copolymerized is 100 weights of the monomer component (a) described above. The value is within the range of 0 parts by weight or 0 to 1 part by weight (excluding 0 parts by weight) with respect to parts.
The reason for this is that the (meth) acrylic acid ester copolymer, which is the component (A) as the adhesive main agent, becomes a carboxyl group catalyst by adjusting the blending ratio of the monomer component (b) within such a range. This is because the action can reduce hydrolysis of the aromatic phosphate ester as a flame retardant. Thereby, it can suppress effectively that the adhesiveness of a flame-retardant adhesive composition falls with time due to the decomposition product of phosphoric acid and phenols produced | generated by hydrolysis.
The type of monomer component (b) is not particularly limited as long as it is a vinyl compound having a carboxyl group in the molecule. For example, vinyl acetate, acrylic acid, methacrylic acid, crotonic acid, maleic acid , Itaconic acid, citraconic acid and the like.

Next, the relationship between the blending ratio of the monomer component (b) and the tackiness of the flame retardant pressure-sensitive adhesive composition will be described with reference to FIG.
That is, in FIG. 2, the horizontal axis takes the blending ratio (parts by weight) of acrylic acid as the monomer component (b) to 100 parts by weight of n-butyl acrylate as the monomer component (a), On the left vertical axis is a characteristic curve A that takes the initial adhesive strength (N / 25 mm) in the obtained flame-retardant pressure-sensitive adhesive composition, and on the right vertical axis is the adhesive force in the obtained flame-retardant pressure-sensitive adhesive composition. A characteristic curve B with the retention rate (%) is shown.
Here, the initial adhesive strength of the flame retardant adhesive composition refers to the adhesive strength of the flame retardant adhesive composition that has been allowed to stand for 7 days under conditions of 23 ° C. and 50% RH and is sufficiently crosslinked. The adhesive strength retention of the flammable pressure-sensitive adhesive composition means the rate of change in pressure-sensitive adhesive strength before and after leaving the flame-retardant pressure-sensitive adhesive composition in a predetermined high-temperature and high-humidity environment. It means the value represented by the calculation formula (1).
Adhesive strength retention (%) = (Adhesive strength after standing / Initial adhesive strength) × 100 (1)
In addition, the flame retardant pressure-sensitive adhesive composition before standing was used after being allowed to stand for 7 days under conditions of 23 ° C. and 50% RH and sufficiently crosslinked.
In addition, details, such as a flame-retardant adhesive composition and the measurement conditions of adhesive force and adhesive force retention, are described in the Examples.

First, as understood from the characteristic curve A, as the blending ratio of acrylic acid increases, the initial adhesive strength in the flame retardant adhesive composition increases.
Therefore, it turns out that acrylic acid contributes to the improvement of the initial stage adhesive force in a flame-retardant adhesive composition.
On the other hand, as understood from the characteristic curve B, as the blending ratio of acrylic acid increases, the adhesive strength retention in the flame retardant pressure-sensitive adhesive composition is rapidly decreased.
More specifically, when the blending ratio of acrylic acid exceeds 1 part by weight with respect to 100 parts by weight of the monomer component (a), the adhesive strength over time in the flame retardant adhesive composition is rapidly increased. It turns out that it will reduce.
Therefore, from the characteristic curves A and B, although the acrylic acid as the monomer component (b) improves the initial adhesive strength, the adhesive strength is decreased over time. It is understood that not preferred.

(1) -3 Monomer component (c)
The (meth) acrylic acid ester copolymer as the component (A) contains a nitrogen-containing vinyl compound, that is, a vinyl compound having a nitrogen atom in the molecule as the monomer component (c) when polymerizing. It is characterized by that.
The reason for this is that the monomer component (c) is not substantially used as the monomer component when the component (A) is copolymerized as described above. This is because even if it is a case, it functions as an alternative component, and can effectively improve the initial and aging adhesiveness.
That is, in the present invention, since a carboxyl group-containing vinyl compound is substantially not used as a monomer component when copolymerizing the component (A), based on a general view, a flame retardant adhesive composition There is a risk that the initial tackiness of the object will be insufficient.
However, if a predetermined amount of a nitrogen-containing vinyl compound is used as the monomer component (c), the monomer component (c) has a polarity higher than a predetermined value. You can get enough.
Furthermore, if it is a monomer component (c), since the hydrolysis of the aromatic phosphate ester as a flame retardant which is the component (B) can be stably suppressed, the adhesiveness is effective over time. Can be maintained.
In addition, depending on the type of the nitrogen-containing vinyl compound as the monomer component (c) when the component (A) is copolymerized, for example, a (meth) acrylic acid ester copolymer using acryloylmorpholine or the like may be used. For example, it can be effectively plasticized by a predetermined aromatic phosphate ester, and can exhibit better adhesive properties in the flame-retardant adhesive composition.

The type of the monomer component (c) is not particularly limited as long as it is a vinyl compound having a nitrogen atom in the molecule. For example, N-methylvinylpyrrolidone, N-vinylpyridine, N- Nitrogen such as vinylpiperidone, N-vinylpyrimidine, N-vinylpiperazine, N-vinylpyrazine, N-vinylpyrrole, N-vinyloxazole, N-vinylmorpholine, N-vinylcaprolactam, N-vinylpyrrolidone, N-vinylimidazole Vinyl compound having a heterocyclic ring: acryloylmorpholine, dimethyl (meth) acrylamide, (meth) acrylamide, N-methyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-methylol (meth) acrylamide, N-hydroxy Ethyl (meth) acrylic (Meth) acrylamide derivatives such as (meth) acrylic acid monomethylaminoethyl, (meth) acrylic acid monoethylaminoethyl, (meth) acrylic acid monomethylaminopropyl, (meth) acrylic acid monoethylaminopropyl ) (Meth) acrylic acid ester containing an amino group such as monoalkylaminoalkyl acrylate; N-vinylacetamide; N-vinylformamide, or a combination of two or more.
The (meth) acrylamide derivative refers to a compound having a structure in which (meth) acrylic acid and an arbitrary secondary or lower amine are bonded with an amide bond.

Among the monomer components (c) described above, the vinyl compound having an amide structure in the molecule more stably suppresses hydrolysis of the aromatic phosphate ester as a flame retardant as the component (B). However, since the adhesiveness of a flame-retardant adhesive composition can be improved more effectively, it is preferable.
Examples of the vinyl compound having such an amide structure include N-vinylpyrrolidone, N-vinylcaprolactam, any (meth) acrylamide derivative, N-vinylacetamide, N-vinylformamide and the like.

Further, among vinyl compounds having an amide structure in the molecule, it is more preferable to use a (meth) acrylamide derivative because copolymerization with the monomer component (a) is easy.
Among them, when copolymerizing (A) component (meth) acrylate copolymer, when using at least one selected from the group consisting of acryloylmorpholine, dimethylacrylamide, and N-isopropylacrylamide, The (meth) acrylic acid ester copolymer is easily plasticized by a predetermined aromatic phosphate ester that is a flame retardant, and can exhibit even better adhesive properties in a flame retardant adhesive composition. The monomer component (c) is a particularly preferable type.

Moreover, the blending ratio of the monomer component (c) when copolymerizing the (meth) acrylic acid ester copolymer as the component (A) is based on 100 parts by weight of the monomer component (a) described above. The value is within the range of 1 to 70 parts by weight.
This is because when the blending ratio of the monomer component (c) is less than 1 part by weight, the tackiness in the flame retardant pressure-sensitive adhesive composition may be insufficient. On the other hand, when the blending ratio of the monomer component (c) exceeds 70 parts by weight, the storage elastic modulus of the obtained flame-retardant pressure-sensitive adhesive composition becomes too large, and desired tackiness is obtained. This is because it may disappear.
Therefore, the blending ratio of the monomer component (c) when copolymerizing the (meth) acrylic acid ester copolymer as the component (A) is 2 with respect to 100 parts by weight of the monomer component (a). It is more preferable to set it as the value within the range of -60 weight part, and it is further more preferable to set it as the value within the range of 10-50 weight part.

Next, the relationship between the blending ratio of the monomer component (c) and the tackiness of the flame retardant pressure-sensitive adhesive composition will be described with reference to FIG.
That is, in FIG. 3, the horizontal axis represents the blending ratio (parts by weight) of acryloylmorpholine as the monomer component (c) to 100 parts by weight of n-butyl acrylate as the monomer component (a). The left vertical axis represents the characteristic curve A that took the initial adhesive strength (N / 25 mm) in the obtained flame-retardant pressure-sensitive adhesive composition, and the right vertical axis represents the adhesion in the obtained flame-retardant pressure-sensitive adhesive composition. Characteristic curves B taking force retention (%) are shown respectively.
The details of the flame retardant pressure-sensitive adhesive composition and the measurement conditions for the pressure-sensitive adhesive strength and the pressure-sensitive adhesive strength retention are described in the examples.

First, as understood from the characteristic curve A, the initial adhesive force in the flame retardant pressure-sensitive adhesive composition is gradually increasing as the blending ratio of acryloylmorpholine increases.
Therefore, it is understood that acryloylmorpholine contributes to the improvement of the initial adhesive strength in the flame retardant pressure-sensitive adhesive composition, although not as much as acrylic acid described with reference to FIG.
In addition, as understood from the characteristic curve B, the adhesive strength retention in the flame retardant adhesive composition stably maintains a high value regardless of the blending ratio of acryloylmorpholine, and FIG. There is no tendency to decrease the adhesive strength retention as in the case of acrylic acid explained using the above.
Therefore, it can be understood from the characteristic curves A and B that acryloylmorpholine as the monomer component (c) can stably maintain the adhesive strength over time while improving the initial adhesive strength.

Moreover, when the blending ratio of acryloylmorpholine as the component (c) is less than 1 part by weight with respect to 100 parts by weight of the monomer component (a), the initial adhesive strength is excessive as shown in the characteristic curve A. May be a low value.
On the other hand, if the amount of acryloylmorpholine as the component (c) is 70 parts by weight or less with respect to 100 parts by weight of the monomer component (a), while improving the initial adhesive force, It has been separately confirmed that the adhesive strength can be stably maintained.
Therefore, it is understood that the blending ratio of acryloylmorpholine as the component (c) is preferably set to a value within the range of 1 to 70 parts by weight with respect to 100 parts by weight of the monomer component (a).

(1) -4 Monomer component (d)
Further, as a further monomer component (d) when copolymerizing the (A) component (meth) acrylate copolymer, it has a hydroxyl group-containing vinyl compound, that is, a hydroxyl group (hydroxyl group) in the molecule. It is preferable that a vinyl compound is included.
The reason for this is that, when the monomer component (d) is further included, when a crosslinking agent described later is added to the flame retardant pressure-sensitive adhesive composition, the (meth) acrylic acid ester copolymers are crosslinked. This is because it can be carried out effectively and the adjustment of the adhesive strength and storage elastic modulus of the flame-retardant pressure-sensitive adhesive composition can be easily performed.

Examples of the monomer component (d) include vinyl compounds having a hydroxyl group in the molecule, such as vinyl alcohol, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate. , (Meth) acrylic acid 3-hydroxypropyl, (meth) acrylic acid 2-hydroxybutyl, (meth) acrylic acid 3-hydroxybutyl, (meth) acrylic acid 4-hydroxybutyl, N-methylol (meth) acrylamide, N -Single type of hydroxyethyl acrylamide etc., or 2 or more types of combinations are mentioned.
In consideration of compatibility with the monomer component (a) which is the main component constituting the component (A), 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate, N- It is particularly preferred that it is either methylol (meth) acrylamide or N-hydroxyethylacrylamide.
In particular, if it is a (meth) acrylamide derivative having a hydroxyl group such as N-methylol (meth) acrylamide or N-hydroxyethylacrylamide, it acts as the monomer component (d) and at the same time as the monomer component (c). Can also work.
Therefore, a flame-retardant pressure-sensitive adhesive composition can be easily prepared without adding the monomer components (c) and (d) separately.

Moreover, the blending ratio of the monomer component (d) when copolymerizing the (meth) acrylic acid ester copolymer as the component (A) is based on 100 parts by weight of the monomer component (a) described above. The value is preferably in the range of 1 to 15 parts by weight.
The reason for this is that when the amount of the monomer component (d) is less than 1 part by weight, sufficient cohesion is obtained when the amount of the aromatic phosphate ester as the flame retardant (B) is increased. It is because it cannot be obtained. On the other hand, when the amount of the monomer component (d) exceeds 15 parts by weight, the tackiness of the flame retardant pressure-sensitive adhesive composition may be excessively lowered.
Accordingly, the blending ratio of the monomer component (d) is more preferably set to a value within the range of 1.5 to 12 parts by weight with respect to 100 parts by weight of the monomer component (a). More preferably, the value is within the range of parts.
In addition, when the flame retardant adhesive composition of the present invention contains a large amount of an aromatic phosphate, it tends to be difficult to obtain a sufficient cohesive force. For this reason, the monomer component (d) may be contained in a larger amount than is usually used.
Therefore, when both of the blending ratios of the monomer components (c) and (d) are increased, the polarity of the (meth) acrylic acid ester copolymer that is the component (A) is unintentionally increased. In some cases, the storage elastic modulus of the flame retardant pressure-sensitive adhesive composition becomes too high.
In this regard, if the (meth) acrylamide derivative having a hydroxyl group, which is a monomer component also serving as the monomer components (c) and (d), the monomer components (c) and (d) are consequently obtained. The total amount of the blending ratio can be reduced, and the above-mentioned problems can be avoided.
In addition, since the monomer components (a) to (d) described above are the main components constituting the (meth) acrylic acid ester copolymer as the component (A), the monomer components ( The sum of the blending ratios of a) to (d) is preferably set to a value of 70% by weight or more of all monomer components constituting the component (A), and is set to a value within the range of 80 to 100% by weight. It is more preferable that the value be in the range of 90 to 95% by weight.

(2) Weight average molecular weight Moreover, it is preferable to make the weight average molecular weight of the (meth) acrylic acid ester copolymer which is (A) component into the value within the range of 100,000-2 million.
This is because when the weight average molecular weight is less than 100,000, the durability of the flame retardant pressure-sensitive adhesive composition may be insufficient. On the other hand, when the weight average molecular weight exceeds 2 million, it may be difficult to suppress a decrease in processability due to an increase in viscosity or the like.
Therefore, it is more preferable to set the polymerization average molecular weight of the (meth) acrylic acid ester copolymer as the component (A) to a value in the range of 300,000 to 1,500,000, and a value in the range of 500,000 to 1,200,000. More preferably.
In addition, this weight average molecular weight can be measured by the gel permeation chromatography (GPC) method by polystyrene conversion.
The (meth) acrylic acid ester copolymer has been described above, but the (meth) acrylic acid ester copolymer as the component (A) in the present invention may be used alone or as a monomer component. Two or more types having different compositions and weight average molecular weights may be used in combination.
Furthermore, the form of copolymerization is not particularly limited, and any of random, block, and graft copolymers may be used.

2. (B) Component: Flame retardant The flame retardant pressure-sensitive adhesive composition of the present invention contains an aromatic phosphate ester (also referred to as an aromatic ring-containing phosphate ester) as the flame retardant as the component (B). It is characterized by that.
The reason for this is that if it is an aromatic phosphate ester, excellent flame retardancy can be obtained while maintaining the safety and transparency of the flame retardant pressure-sensitive adhesive composition.
That is, if it is an aromatic phosphate ester, unlike conventional halogen compounds, it does not generate halogen gases that are toxic to the human body during combustion, and is compatible with (meth) acrylic acid ester copolymers. This is because it can be easily used even for articles that require transparency.
On the other hand, aromatic phosphate esters can effectively exert radical trapping effects in the gas phase in the combustion field, and also effectively form char in the solid phase, thereby insulating and blocking oxygen. This is because the effect can be exhibited.
The formation of char means that hydrogen or oxygen in the polymer in the composition is extracted during combustion to carbonize the polymer to form an incombustible carbonized film.

Such aromatic phosphate esters are roughly classified into a condensed type and a non-condensed type. In the present invention, either type of aromatic phosphate ester can be used.
More specifically, examples of the condensed aromatic phosphate ester include 1,3-phenylene bis (dixylenyl phosphate), bisphenol A bis (diphenyl phosphate), and 1,3-phenylene bis (diphenyl phosphate). One kind alone or a combination of two or more kinds may be mentioned.
Examples of non-condensable aromatic phosphate esters include triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl 2,6-xylenyl phosphate and 2-ethylhexyl diphenyl phosphate. One kind alone or a combination of two or more kinds may be mentioned.

Further, the blending amount of the flame retardant as the component (B) is set to a value within the range of 70 to 200 parts by weight with respect to 100 parts by weight of the (meth) acrylic acid ester copolymer as the component (A). It is characterized by.
This is because, by setting the blending amount of the flame retardant as the component (B) within such a range, the phenomenon that the flame retardant precipitates on the surface of the flame retardant adhesive composition, so-called blooming, is effectively suppressed. This is because excellent flame retardancy can be obtained while stably maintaining transparency and adhesiveness.
That is, when the blending amount is less than 70 parts by weight, the effect of adding the flame retardant is not sufficiently exhibited, and it may be difficult to obtain desired flame retardancy. On the other hand, when the blending amount exceeds 200 parts by weight, it may be difficult to obtain a sufficient cohesive force.
Therefore, the blending amount of the flame retardant as the component (B) is set to a value within the range of 75 to 180 parts by weight with respect to 100 parts by weight of the (meth) acrylic acid ester copolymer as the component (A). Is more preferable, and a value within the range of 80 to 170 parts by weight is even more preferable.

In addition, at least one of the aromatic phosphates is preferably a liquid aromatic phosphate, that is, an aromatic phosphate that is liquid at 25 ° C.
This is because such a liquid aromatic phosphate ester can more effectively suppress the occurrence of blooming.
Examples of the type of aromatic phosphate that is liquid at 25 ° C. include bisphenol A bis (diphenyl phosphate), tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl 2,6-xylate. Examples thereof include nyl phosphate, 2-ethylhexyl diphenyl phosphate, 1,3-phenylenebis (diphenyl phosphate) and the like alone or in combination of two or more.
The viscosity (measured at 25 ° C.) of the liquid aromatic phosphate is preferably 50000 mPa · sec or less, more preferably 10 to 30000 mPa · sec, and more preferably 100 to 25000 mPa · sec. More preferably, the value is within the range of sec.

Moreover, it is preferable that the aromatic phosphate ester that is liquid at 25 ° C. is a condensed liquid aromatic phosphate ester.
This is because, when non-condensed liquid aromatic phosphate ester is used, the occurrence of blooming can be effectively suppressed, but the flame retardancy may be inferior.
On the other hand, the condensed liquid aromatic phosphate ester is excellent in flame retardancy while effectively suppressing blooming.
Examples of the condensed liquid aromatic phosphate ester include bisphenol A bis (diphenyl phosphate).

Moreover, it is preferable to make the compounding quantity of liquid aromatic phosphate ester into the value of 30 weight% or more with respect to the whole quantity of the flame retardant which is (B) component.
The reason for this is that if the blending amount is less than 30% by weight, it may be difficult to effectively suppress blooming due to the flame retardant.
Further, by using a predetermined amount of such a liquid aromatic phosphate ester, the flame retardant pressure-sensitive adhesive composition exhibits a plastic effect on the nitrogen-containing vinyl compound (c), for example, acryloylmorpholine. This is because the adhesive properties in can be further improved.
Accordingly, the blending amount of the liquid aromatic phosphate ester is more preferably set to a value within the range of 50 to 100% by weight, based on the total amount of the flame retardant as the component (B), and is 70 to 90% by weight. It is more preferable to set the value within the range.

Further, it has been confirmed that the liquid aromatic phosphate not only functions as a flame retardant, but also functions as a plasticizer for the (meth) acrylic acid ester copolymer.
And the function as a plasticizer of this liquid aromatic phosphate ester is to the compounding quantity of the nitrogen-containing vinyl compound as a monomer component (c) in the (meth) acrylic acid ester copolymer which is (A) component. On the other hand, it has been confirmed that it depends heavily.
Hereinafter, the function of the liquid aromatic phosphate ester as a plasticizer will be specifically described with reference to FIG.
In FIG. 4, the horizontal axis represents the blending amount (part by weight) of the liquid aromatic phosphate ester with respect to 100 parts by weight of the (meth) acrylic acid ester copolymer as the component (A), and the vertical axis represents In addition, characteristic curves A and B taking the initial adhesive strength (N / 25 mm) in the flame retardant adhesive composition are shown.
The characteristic curve A shows that the (meth) acrylic acid ester copolymer used as the component (A) is composed of n-butyl acrylate as the monomer component (a) and monomer component (c). (Example 7) is a characteristic curve when the mixing ratio (weight ratio) of monomer component (a): monomer component (c) is 100: 55.6. Equivalent to Comparative Examples 8-10).
As in Comparative Examples 8 and 9, when the initial adhesive force was zipped (vibration phenomenon seen in the adhesive force measurement chart within a certain range), the average value of the upper and lower limit values was initially set. Plotted as adhesion.
On the other hand, the characteristic curve B shows that the (meth) acrylic acid ester copolymer used as the component (A) is composed of n-butyl acrylate as the monomer component (a) and monomer component (c). (Example 4) This is a characteristic curve when the mixing ratio (weight ratio) of monomer component (a): monomer component (c) is 100: 11.4. Equivalent to Comparative Example 11).
In addition, bisphenol A bis (diphenyl phosphate) was used as the liquid aromatic phosphate ester, and other flame retardants were not used in combination.
In addition, the details of the flame-retardant pressure-sensitive adhesive composition, the measurement conditions for the adhesive strength, and the like are the same as those in Example 1.

First, looking at the characteristic curve A, when the blending ratio (weight ratio) of monomer component (a): monomer component (c) is 100: 55.6, blending of liquid aromatic phosphate ester As the amount increases from 0 parts by weight to 70 parts by weight or more, the initial adhesive strength in the flame retardant adhesive composition rapidly increases from a value of about 1 N / 25 mm to a value of about 15 N / 25 mm. It can be seen that it increases.
The reason why the characteristic curve A exhibits such behavior is that when the blending ratio of the monomer component (c) is a predetermined value or more, the flame retardant adhesive is caused by the polarity of the monomer component (c). This is because the cohesive force of the agent composition is excessively increased.
Therefore, if the use of the plasticizer is omitted or the blending amount of the plasticizer is excessively insufficient, it is difficult to obtain a desired initial adhesive force.
Therefore, when the blending ratio of the monomer component (c) is a predetermined value or more, the characteristic curve A is shown by increasing the blending amount of the liquid aromatic phosphate having a function as a plasticizer. Thus, the initial adhesive strength of the flame retardant pressure-sensitive adhesive composition can be effectively improved to a value of around 15 N / 25 mm, and the desired flame retardancy can also be obtained together. become.

On the other hand, when the characteristic curve B is seen, when the blending ratio (weight ratio) of monomer component (a): monomer component (c) is 100: 11.4, blending of liquid aromatic phosphate ester Even if the amount is increased from 0 parts by weight to 70 parts by weight or more, the initial adhesive force of the flame retardant adhesive only decreases moderately. Moreover, it can be seen that only a relatively low initial adhesive strength of about 5 to 9 N / 25 mm can be obtained.
The reason why the characteristic curve B exhibits such a behavior is that when the blending ratio of the monomer component (c) is a value less than a predetermined value, even if the use of a plasticizer is omitted, the flame retardant adhesive While the cohesive force of the adhesive composition is moderately maintained and the stress of the flame retardant adhesive composition against shearing is maintained, the increase in the amount of plasticizer causes a significant decrease in cohesive force. It is presumed that the stress of the flame retardant pressure-sensitive adhesive composition is weakened, and this stress reduction greatly contributes to the reduction of the adhesive strength.
As a result, when such a (meth) acrylate copolymer having a small absolute amount of the monomer component (c) is used, only a relatively low initial adhesive strength of about 5 to 9 N / 25 mm is obtained. It will not be possible.

From the above, in order to obtain a flame retardant pressure-sensitive adhesive composition having a relatively high initial adhesive strength of about 15 N / 25 mm, with the blending ratio of the nitrogen-containing vinyl compound as the monomer component (c) being a predetermined value or more. It is understood that it is preferable to use a liquid aromatic phosphate ester having a function as a plasticizer as a flame retardant.
In addition, in obtaining a flame-retardant pressure-sensitive adhesive composition having a relatively high initial adhesive strength, the blending of the monomer component (c) that makes it effective to use a liquid aromatic phosphate having a function as a plasticizer It has been confirmed that the amount is 15 parts by weight or more with respect to 100 parts by weight of the monomer component (a).
Therefore, in order to obtain a better initial adhesive strength, the blending amount of the monomer component (c) is set to a value within the range of 16 to 70 parts by weight with respect to 100 parts by weight of the monomer component (a). It is more preferable to set the value within the range of 18 to 70 parts by weight.

In addition, if it is a range which does not impair the effect of this invention, you may further contain aromatic phosphate ester which is solid in 25 degreeC as aromatic phosphate ester.
Examples of the aromatic phosphate ester that is solid at 25 ° C. include one kind alone or a combination of two or more kinds such as 1,3-phenylenebis (dixylenyl phosphate) and triphenyl phosphate.
In addition, the flame retardant as the component (B) may contain other flame retardants in addition to the aromatic phosphate ester as long as the effects of the present invention are not impaired.
As other flame retardants, for example, phosphorus element-containing compounds such as phosphazene and ammonium polyphosphate are preferably used.

3. Ingredient (C): Crosslinking agent Moreover, in constituting the flame-retardant pressure-sensitive adhesive composition of the present invention, it is preferable that a crosslinking agent is contained as the (C) component.
The reason for this is that the (meth) acrylic acid ester copolymer (A) component is cross-linked with the cross-linking agent (C) component, so that the adhesive strength and storage elastic modulus of the flame-retardant pressure-sensitive adhesive composition. This is because the adjustment can be easily performed.

(1) Kind Moreover, as this crosslinking agent, an isocyanate type crosslinking agent, an aziridine type crosslinking agent, an epoxy-type crosslinking agent, and a metal chelate type crosslinking agent can be mentioned preferably.
This reason is because the adhesive force and storage elastic modulus of a flame-retardant adhesive composition can be adjusted to a more suitable range by including these crosslinking agents.
In particular, in the case of an isocyanate-based crosslinking agent, when the (meth) acrylate copolymer contains a vinyl compound having a hydroxyl group in the molecule as the monomer component (d), the hydroxyl group This is because (meth) acrylic acid ester copolymers can be effectively chemically cross-linked with each other.

  Specific examples of such isocyanate crosslinking agents include, for example, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3- Aliphatic diisocyanates such as butylene diisocyanate, 1,3-butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methyl caproate, such as 1,3-cyclo Pentane diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate 4,4'-methylenebis (cyclohexyl isocyanate), methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 1,4-bis (isocyanatomethyl) cyclohexane, 1,3-bis (isocyanate methyl) Cycloaliphatic diisocyanates such as cyclohexane, for example m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4- or 2, Aromatic dii such as 6-tolylene diisocyanate or mixtures thereof, 4,4'-toluidine diisocyanate, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate Cyanates such as 1,3- or 1,4-xylylene diisocyanate or mixtures thereof, ω, ω′-diisocyanate-1,4-diethylbenzene, 1,3- or 1,4-bis (1-isocyanate-1- Araliphatic diisocyanates such as methylethyl) benzene or mixtures thereof such as triphenylmethane-4,4 ′, 4 ″ -triisocyanate, 1,3,5-triisocyanatebenzene, 2,4,6-triisocyanate toluene Triisocyanates such as 1,3,5-triisocyanate hexane, for example, polyisocyanate monomers such as 4,4′-diphenyldimethylmethane-2,2′-5,5′-tetraisocyanate, the above-mentioned polyisocyanates Monomers derived dimers, trimers, biurets, alofs Polyisocyanate having 2,4,6-oxadiazinetrione ring obtained from nate, carbon dioxide and the above-mentioned polyisocyanate monomer, such as ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, 1,6 -Hexane glycol, 3-methyl-1,5-pentanediol, 3,3'-dimethylol heptane, cyclohexanedimethanol, diethylene glycol, triethylene glycol, dipropylene glycol, glycerol, trimethylolpropane, pentaerythritol, sorbitol, etc. Adducts of low molecular weight polyols having a weight average molecular weight of less than 200 to the above-mentioned various isocyanates, such as polyester polyols having a molecular weight of 200 to 200,000, polyether polyethers Examples include adducts to the above-mentioned various isocyanates such as all, polyether ester polyol, polyester amide polyol, polycaprolactone polyol, polyvalerolactone polyol, acrylic polyol, polycarbonate polyol, polyhydroxyalkane, castor oil, and polyurethane polyol.

(2) Compounding quantity Moreover, the compounding quantity of the crosslinking agent as (C) component is 0.01-20 weight part with respect to 100 weight part of the (meth) acrylic acid ester copolymer which is (A) component. A value within the range is preferable.
The reason for this is that when the blending amount of the cross-linking agent is less than 0.01 parts by weight, the cohesive force is excessively reduced by the addition of the aromatic phosphate ester as the flame retardant as the component (B). This is because it may be difficult to obtain sufficient adhesive strength and storage elastic modulus.
On the other hand, when the blending amount of the cross-linking agent exceeds 20 parts by weight, the cross-linking of the (meth) acrylic acid ester copolymers becomes excessive, and conversely, the adhesive force tends to decrease. Because.
In order to obtain the above results, the amount of the crosslinking agent as the component (C) is 0.1 to 18 weights with respect to 100 parts by weight of the (meth) acrylic acid ester copolymer as the component (A). The value is more preferably in the range of parts by weight, and further preferably in the range of 0.3 to 15 parts by weight.
The cross-linking agent may be added as a solution or dispersed in a solvent as necessary. In that case, the amount containing the solvent may be indicated as the amount of the cross-linking agent. The blending amount in indicates the amount of the crosslinking agent itself (solid content) as the component (C) not containing a solvent.

4). Diluting solvent In the flame-retardant pressure-sensitive adhesive composition of the present invention, the viewpoint of improving the dispersibility of each component or adjusting the viscosity to an appropriate value when applying the flame-retardant pressure-sensitive adhesive composition to a release film or the like. From this, a solvent can be used.
As such a solvent, for example, toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, ethyl isobutyl ketone, methyl alcohol, ethyl alcohol, isopropyl alcohol and the like are preferable. The concentration of the pressure-sensitive adhesive composition when the solvent is added is 5 A value in the range of ˜70% by weight is preferable.

5. Additives Other additives include flame retardant adhesive compositions, tackifiers, antioxidants, UV absorbers, light stabilizers, softeners, fillers, high refractive index agents, diffusing agents. Etc. are also preferably contained.
Moreover, in that case, although it depends on the kind of the additive, the blending amount is in the range of 0.1 to 20 parts by weight with respect to 100 parts by weight of the (meth) acrylate copolymer as the component (A). It is preferable to set the value within the range.

6). Flame-retardant pressure-sensitive adhesive layer The flame-retardant pressure-sensitive adhesive composition can be constituted as a flame-retardant pressure-sensitive adhesive layer through the following steps (1) to (3).
(1) A flame retardant pressure-sensitive adhesive composition comprising a (meth) acrylic acid ester copolymer as the component (A) and a flame retardant as the component (B), which is difficult to be the component (B) While a flame retardant contains aromatic phosphate ester, the compounding quantity of the flame retardant which is (B) component is 70-200 with respect to 100 weight part of (A) component (meth) acrylic acid ester copolymers. The following monomer components (a) to (c) are used as monomer components when copolymerizing the (meth) acrylic acid ester copolymer as the component (A) with a value within the range of parts by weight. (A) (meth) acrylic ester having 1 to 12 carbon atoms of alkyl group: 100 parts by weight (b) carboxyl group-containing vinyl compound: 0 part by weight or 0 to 1 part by weight (however, 0 part by weight is not included) )
(C) Nitrogen-containing vinyl compound: 1 to 70 parts by weight (2) Step of applying a flame retardant pressure-sensitive adhesive composition to a substrate to form an application layer (3) Flame retardant pressure-sensitive adhesive composition The step of cross-linking and forming the coating layer as a flame-retardant pressure-sensitive adhesive layer Hereinafter, the steps leading to the construction of the flame-retardant pressure-sensitive adhesive layer will be specifically described with reference to the drawings as appropriate.

(1) Process (1) (Preparation process of a flame-retardant adhesive composition)
Specifically, in the step (1), it is preferable to first copolymerize the monomer components (a) to (c) to obtain a (meth) acrylic acid ester copolymer as the component (A).
The copolymerization method is not particularly limited as long as it is a conventionally known polymerization method, but it is preferable to employ solution polymerization.
Moreover, as a solvent used when performing solution polymerization, what was mentioned as a dilution solvent of the flame-retardant adhesive composition mentioned above can be used, However, It is preferable to use toluene and ethyl acetate especially.
Moreover, it is preferable to add a polymerization initiator when carrying out the copolymerization.
Such a polymerization initiator is not particularly limited as long as it is a conventionally known polymerization initiator, but an azo polymerization initiator is preferably used.
Moreover, the (meth) acrylic acid ester copolymer which is (A) component can be diluted to arbitrary solid content for the purpose of the improvement of the handleability in the process of a process (1) transfer, and workability.
In addition, as a dilution solvent, the dilution solvent mentioned above can be used in the range which does not prevent compatibility with the solution used for solution polymerization.
Next, to the component (A) in the obtained solvent, an aromatic phosphate ester as a flame retardant as the component (B) and a crosslinking agent as the component (C) are added. It is preferable to obtain a solution of the flammable adhesive composition.

(2) Step (2) (Applying step of flame retardant adhesive composition)
Step (2) is a step of forming the coating layer 1 by applying the flame retardant pressure-sensitive adhesive composition to the substrate 2 as shown in FIG.
Such a substrate is preferably a release film, for example, a polyester film such as polyethylene terephthalate, polybutylene terephthalate, or polyethylene naphthalate, or a polyolefin film such as polypropylene or polyethylene, such as a silicone resin, a fluororesin, or an alkyd resin. The thing which applied the agent and provided the peeling layer is mentioned.
In addition, it is preferable that the thickness of this release film is usually a value within the range of 20 to 150 μm.

Examples of the method for applying the flame retardant pressure-sensitive adhesive composition on the substrate include a bar coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, and a gravure coating method. It is preferable to dry after applying the flame retardant pressure-sensitive adhesive composition to which is added to form a coating layer (coating film).
At this time, the thickness of the coating layer is preferably set to a value in the range of 1 to 100 μm and more preferably set to a value in the range of 5 to 50 μm on the basis of drying.
This is because if the coating layer is too thin, sufficient adhesive properties may not be obtained. Conversely, if the coating layer is too thick, the residual solvent may cause a problem.
Moreover, as drying conditions, it is usually preferable to set it within a range of 10 to 10 minutes at 50 to 150 ° C.

(3) Step (3) (Coating layer crosslinking step)
Step (3) is a step of crosslinking the flame retardant pressure-sensitive adhesive composition to make the coating layer a flame retardant pressure-sensitive adhesive layer.
That is, as shown in FIG.1 (b), the state which laminated | stacked the tape base material 101 etc. as another base material with respect to the surface of the application layer 1 of the state dried on the peeling film 2 as a base material It is preferable to crosslink with a flame retardant pressure-sensitive adhesive layer 10.
The crosslinking is performed through the above-described coating layer drying step and seasoning step.
Examples of the conditions and period of the seasoning step include conditions such as those in Examples described later, but are not particularly limited.

[Second Embodiment]
The second embodiment of the present invention comprises a flame retardant comprising a (meth) acrylic acid ester copolymer as the component (A) and a flame retardant as the component (B) on one or both sides of the substrate. A flame-retardant pressure-sensitive adhesive tape comprising the pressure-sensitive adhesive composition as a pressure-sensitive adhesive layer, wherein the flame retardant as the component (B) contains an aromatic phosphate and the amount of the flame retardant as the component (B) Is a value within the range of 70 to 200 parts by weight with respect to 100 parts by weight of the (meth) acrylic acid ester copolymer as the component (A), and the (meth) acrylic acid ester as the component (A) A flame retardant pressure-sensitive adhesive tape comprising the following components (a) to (c) as monomer components for copolymerizing a copolymer.
(A) (meth) acrylic acid alkyl ester having 1 to 12 carbon atoms of alkyl group: 100 parts by weight (b) carboxyl group-containing vinyl compound: 0 part by weight or 0 to 1 part by weight (provided that 0 part by weight is included) Absent.)
(C) Nitrogen-containing vinyl compound: 1 to 70 parts by weight Hereinafter, the second embodiment of the present invention will be specifically described with reference to FIG. 1 with a focus on differences from the first embodiment.

1. Tape base material In the flame-retardant pressure-sensitive adhesive tape of the present invention, the base material is a tape base material, and at least one of the tape base materials is provided with the flame-retardant pressure-sensitive adhesive layer described in the first embodiment. It is characterized by.
Moreover, as a material substance of this tape base material, if it can be used for the use as a tape, it will not restrict | limit in particular.
Thus, for example, polyethylene terephthalate film, polyethylene naphthalate film, polybutylene terephthalate film, polyimide film, polyetherimide film, polyaramid, polyether ketone, polyether ether ketone, polyphenylene sulfide, poly (4-methylpentene-1) And a polyolefin film having heat resistance.
In order to improve the flame retardancy of the tape substrate, the tape substrate may contain a flame retardant such as an aromatic phosphate ester, phosphate ester, metal hydrate, polyimide, polyetherimide, A highly flame-retardant coating material such as polyaramid or polyphenylene sulfite may be applied.

Moreover, although the thickness of a tape base material changes a little with materials to be used and a use, it is usually preferable to set it as the value within the range of 3-300 micrometers, and set it as the value within the range of 5-100 micrometers. More preferred.
Moreover, about the width | variety of a tape base material, although it can be set as a suitable width according to the use of a tape, Usually, it is preferable to set it as the value within the range of 3-200 mm.
Moreover, after passing through the process of forming a flame retardant adhesive layer on a tape base material using a tape base material having a width of 10 mm to 10 m, or the step of laminating a tape base material on a flame retardant adhesive layer, The flame retardant pressure-sensitive adhesive layer-attached tape substrate may be cut into the appropriate width described above.

Moreover, it is also preferable that the surface side in which the coating layer of a tape base material is formed is surface-treated.
Examples of such surface treatment include primer treatment, corona treatment, flame treatment and the like, and primer treatment is particularly preferable.
This is because the adhesion of the flame-retardant pressure-sensitive adhesive layer to the tape substrate can be further improved by using a tape substrate on which such a primer layer is formed.
In addition, as a material constituting such a primer layer, cellulose ester (for example, cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose nitrate, and combinations thereof), polyacryl, polyurethane, polyvinyl alcohol , Polyvinyl ester, polyvinyl acetal, polyvinyl ether, polyvinyl ketone, polyvinyl carbazole, polyvinyl butyral, and combinations thereof.
Further, the thickness of the primer layer is not particularly limited, but it is usually preferable to set the value within a range of 0.05 μm to 10 μm.

2. 1. Flame-retardant adhesive layer Moreover, as shown in FIG. 1, the flame-retardant adhesive layer 10 in the flame-retardant adhesive tape 100 of this invention is the specific flame-retardant adhesive composition described as 1st Embodiment. It is characterized by setting it as a flame-retardant adhesive layer which consists of a thing.
In addition, about the specific content of this flame-retardant adhesive layer, since it can be made to be the same as that already demonstrated in 1st Embodiment, description here is abbreviate | omitted.

Moreover, it is preferable to make the thickness of this flame-retardant adhesive layer into the value within the range of 1-100 micrometers.
This is because, by setting the thickness of the flame-retardant pressure-sensitive adhesive layer in such a range, the pressure-sensitive adhesive properties such as desired adhesive strength and storage elastic modulus can be more stably exhibited. That is, when the thickness is less than 1 μm, it is difficult to express a desired adhesive force, and problems such as floating and peeling may easily occur.
On the other hand, when the thickness exceeds 100 μm, problems such as adherend contamination and adhesive residue may easily occur.
Therefore, the thickness of the flame retardant pressure-sensitive adhesive layer is more preferably set to a value within the range of 5 to 70 μm, and further preferably set to a value within the range of 10 to 50 μm.

Moreover, as a formation method of the flame-retardant adhesive layer with respect to a tape base material, as shown to FIG.1 (a)-(c), the peeling film in the application layer 1 formed on the peeling film 2 as a base material It is preferable that the surface on the side without 2 is directly adhered to the tape base material 101 as another base material, and then laminated, and then cross-linked to obtain the flame retardant pressure-sensitive adhesive tape 100a.
Or you may make it laminate | stack with respect to a tape base material, after making the flame retardant adhesive composition apply | coated on the peeling film previously bridge | crosslink and setting it as a flame retardant adhesive layer.
Moreover, as a method of bonding the obtained flame-retardant pressure-sensitive adhesive tape to the adherend, first, the flame-retardant pressure-sensitive adhesive layer 10 is laminated as shown in FIGS. It is preferable that the release film 2 is peeled off and then bonded by bringing the surface of the flame retardant pressure-sensitive adhesive layer 10 that has appeared into close contact with the adherend.
In addition, lamination | stacking of the flame-retardant adhesive composition with respect to this tape base material may be laminated | stacked only on the single side | surface of a tape base material, it laminates | stacks on both surfaces, and it will adhere to an adherend in any surface of a tape. You may enable it to paste.
The flame-retardant pressure-sensitive adhesive tape thus obtained is mainly used for locking, sealing, and adhering articles. For example, tape for insulating electronic components and tape for fixing / bundling in electronic devices, etc. It is suitably used for

3. Adhesive strength retention rate From the initial adhesive strength of the flame retardant tape measured according to JIS Z 0237 and the adhesive strength after standing for 7 days in an environment of 60 ° C. and 95% RH, the following calculation is performed. It is preferable to set the adhesive strength retention (%) calculated using the formula (1) to a value within the range of 75 to 125%.
Adhesive strength retention (%) = (Adhesive strength after standing / Initial adhesive strength) × 100 (1)
The reason for this is that by controlling the adhesive strength retention rate in this way, it is possible to stably manage the production of a flame-retardant tape with little change in adhesive strength.
That is, it can be used more suitably for applications such as insulating tapes for electronic parts and tapes for fixing and binding in electronic devices.
However, if the value of the adhesive strength retention rate (%) becomes excessively large, the yield at the time of manufacturing the flame-retardant tape may be remarkably reduced, or the types of usable raw materials may be excessively limited.
Therefore, it is more preferable to set the value of the adhesive strength retention (%) in the flame-retardant tape to a value within the range of 80 to 120%, and even more preferable to set the value within the range of 90 to 110%.

[Third Embodiment]
The third embodiment of the present invention comprises a flame retardant containing (meth) acrylic acid ester copolymer as component (A) and a flame retardant as component (B) on one or both sides of the substrate. A flame-retardant pressure-sensitive adhesive sheet comprising the pressure-sensitive adhesive composition as a pressure-sensitive adhesive layer, wherein the flame retardant as the component (B) contains an aromatic phosphate and the amount of the flame retardant as the component (B) Is a value within the range of 70 to 200 parts by weight with respect to 100 parts by weight of the (meth) acrylic acid ester copolymer as the component (A), and the (meth) acrylic acid ester as the component (A) A flame-retardant pressure-sensitive adhesive sheet comprising the following components (a) to (c) as monomer components for copolymerizing a copolymer.
(A) (meth) acrylic acid alkyl ester having 1 to 12 carbon atoms of alkyl group: 100 parts by weight (b) carboxyl group-containing vinyl compound: 0 part by weight or 0 to 1 part by weight (provided that 0 part by weight is included) Absent.)
(C) Nitrogen-containing vinyl compound: 1 to 70 parts by weight Hereinafter, the third embodiment of the present invention will be specifically described focusing on differences from the first and second embodiments.

In the flame-retardant pressure-sensitive adhesive sheet of the present invention, the substrate is a sheet substrate, and the flame-retardant pressure-sensitive adhesive layer described in the first embodiment is provided on at least one of the sheet substrates. To do.
Further, regarding the material material of the sheet base material, the thickness and surface treatment of the sheet base material, and the flame retardant pressure-sensitive adhesive layer, basically, the tape base in the flame retardant pressure-sensitive adhesive tape as the second embodiment is used. It can be the same as that of a material and a flame-retardant adhesive layer.

As described later, the flame retardant pressure-sensitive adhesive sheet, the flame retardant adhesive tape, since the application is significantly different, the area of the sheet base material in the flame retardant pressure-sensitive adhesive sheet is generally of 1 cm ² through 10m ² A value within the range is preferable, and a value within the range of 3 cm ^{2 to 5} m ² is more preferable.
Further, the planar shape of the sheet base material is not limited in any way, for example, from a simple shape such as a rectangle, a circle, an ellipse, and a triangle, to a complicated shape appropriately corresponding to the surface shape of the adherend. Further, a perforated portion or a cut portion may be provided in the plane.

  The flame-retardant pressure-sensitive adhesive sheet obtained in this way can be used for information display labels, labels or sheets for the purpose of imparting design properties, for example, quality display labels for flameproof articles, wallpaper, Used for applications such as information display labels for electronic equipment casings or parts.

  Hereinafter, the present invention will be described in more detail with reference to examples.

[Example 1]
1. Preparation of flame retardant pressure-sensitive adhesive composition 100 parts by weight of (meth) acrylic acid ester copolymer as component (A) below, 80 parts by weight of flame retardant as component (B), and crosslinking as component (C) A flame retardant pressure-sensitive adhesive composition was prepared from 3.6 parts by weight of the agent. In addition, the numerical value in Table 1 shows the value converted into solid content.
In Table 1, the blending ratio of the monomer components (a) to (d) means parts by weight when the whole monomer component is 100 parts by weight. It means parts by weight when the component (a) is 100 parts by weight.
Furthermore, the compounding quantity of (B) and (C) component means the weight part when (A) component is 100 weight part.

(1) Component (A) In a nitrogen atmosphere, 80 parts by weight of n-butyl acrylate (BA) as the monomer component (a) and acryloyl morpholine as the monomer component (c) are placed in a container. 18 parts by weight of phosphorus (ACMO), 2 parts by weight of 2-hydroxyethyl acrylate (HEA) as the monomer component (d), 0.3 parts by weight of azobisisobutyronitrile as a polymerization initiator, 150 parts by weight of ethyl acetate as a solvent was accommodated.
Next, polymerization was carried out at 60 ° C. for 8 hours to obtain a (meth) acrylic acid ester copolymer solution having a weight average molecular weight of 600,000. Next, the resulting (meth) acrylic acid ester copolymer solution was diluted by adding ethyl acetate while stirring the solution until the solid content became 35% by weight, and (meth) acrylic as the component (A). A solution having a solid content of 35% by weight in which the acid ester copolymer was dissolved in ethyl acetate was obtained.
In addition, the weight average molecular weight of the (meth) acrylic acid ester copolymer was measured by a gel permeation chromatography method (hereinafter abbreviated as GPC method).
That is, first, a calibration curve was prepared using polystyrene. Hereinafter, the weight average molecular weight is expressed in terms of polystyrene. Then, (meth) concentration of the measurement object such as an acrylic acid ester copolymer is prepared 1 weight percent of tetrahydrofuran (THF) solution, manufactured by Tosoh Corporation, GEL PER MEATION CHROMATOGRAPH HLC-8020 (TSK GEL GMH XL, The weight average molecular weight was measured using a TSK _GEL GMH _XL and a TSK _GEL G2000 _HXL triple column) under the conditions of 40 ° C., THF solvent and 1 ml / min. Then, TSK GUARD COLUMN manufactured by Tosoh Corporation was used as a guard column.

(2) About (B) component The liquid aromatic as (B) component with respect to 100 weight part of (meth) acrylic acid ester copolymer solutions (solid content 35 weight%) as the obtained (A) component. 28 parts by weight of bisphenol A bis (diphenyl phosphate) (manufactured by ADEKA Co., Ltd., FP-600, solid content 100% by weight), which is a kind of phosphate ester, was added.
That is, 80 parts by weight of bisphenol A bis (diphenyl phosphate) as the component (B) was added to 100 parts by weight of the (meth) acrylic acid ester copolymer as the component (A).
In the following description, the component (B) described above may be referred to as FP-600.

(3) About (C) component Furthermore, with respect to 100 parts by weight of the (meth) acrylic acid ester copolymer solution (solid content 35% by weight) as the obtained (A) component, A range isocyanate-based crosslinking agent (manufactured by Toyo Ink Mfg. Co., Ltd., BXX5640, solid content 35% by weight) was added at the same time as the above-described component (B) and 3.6 parts by weight as a solvent-containing amount. To obtain a flame retardant adhesive composition solution.
That is, 3.6 parts by weight of xylene diisocyanate-based cross-linking agent as component (C) was added to 100 parts by weight of (meth) acrylic acid ester copolymer as component (A).
Hereinafter, the component (C) described above may be referred to as BXX5640.

2. Application of Flame Retardant Adhesive Composition Solution Next, the obtained flame retardant adhesive was applied to the release-treated surface of a release film made of polyethylene terephthalate having a thickness of 38 μm as a release film (SP-PET 381031 manufactured by Lintec Corporation). The agent composition solution was applied using a roll knife coater so that the thickness after drying was 20 μm.
Next, after drying at 90 ° C. for 1 minute, it was laminated on a polyimide film (Toray DuPont, Kapton 100H, thickness 25 μm) as a tape base material.
Separately from this, the flame-retardant pressure-sensitive adhesive composition after drying at 90 ° C. for 1 minute was applied to a polyethylene terephthalate film (Toray Co., Ltd., Lumirror 50T60, thickness 50 μm) as a tape base material. Then, lamination was performed in the same manner as described above.

3. Seasoning of the flame retardant pressure-sensitive adhesive composition Next, two types of laminates composed of the coating layer of the flame retardant pressure-sensitive adhesive composition obtained as described above and a tape base material were prepared at 23 ° C. and 50 ° C., respectively. As a flame retardant adhesive tape of Example 1, the tape base material is a polyimide film by allowing it to stand (seasoning) for 7 days under the condition of% RH (relative humidity) to sufficiently crosslink the flame retardant adhesive composition. Two types of flame retardant pressure-sensitive adhesive tapes were obtained, one being a polyethylene terephthalate film and the other being a polyethylene terephthalate film.

4). Evaluation (1) Evaluation of blooming In the flame-retardant adhesive tape using a polyethylene terephthalate film as a tape base material, the occurrence of blooming due to the flame retardant in the flame-retardant adhesive layer was evaluated.
That is, after the flame-retardant pressure-sensitive adhesive tape described above is allowed to stand for 7 days in an environment of 23 ° C. and 50% RH, it is visually determined whether or not aggregates such as crystals are present in the flame-retardant pressure-sensitive adhesive layer. And evaluated according to the following criteria. The obtained results are shown in Table 2.
○: Aggregates are not confirmed ×: Aggregates are confirmed

(2) Flame-retardant evaluation In the flame-retardant adhesive tape which used the polyimide film as a tape base material, the flame retardance of the flame-retardant adhesive tape was evaluated.
That is, after peeling the release film from the flame retardant adhesive tape described above, the UL94VTM rank was determined according to the vertical combustion test method of the plastic material flammability test standard UL94 issued by Under Laboratories. Moreover, at this time, the case where it did not adapt to any of VTM-0-2 was determined to be unacceptable. The obtained results are shown in Table 2.
In addition, the VTM rank of UL94 standard means that VTM-0 has the most excellent flame retardancy, and the flame retardancy decreases as VTM-1 and VTM-2.

(3) Evaluation of adhesiveness In the flame-retardant adhesive tape using a polyethylene terephthalate film as a tape base material, the adhesiveness of the flame-retardant adhesive tape was evaluated.
That is, the initial adhesive strength of the flame retardant tape described above and the adhesive strength (N / 25 mm) to the SUS plate after being left in an environment of 60 ° C. and 95% RH for 7 days were measured according to JIS Z 0237. The adhesive strength retention (%) was calculated using the following calculation formula (1) and evaluated according to the following criteria. The obtained results are shown in Table 2.
Adhesive strength retention (%) = (Adhesive strength after standing / Initial adhesive strength) × 100 (1)
A: Adhesive strength holding value is in the range of 90 to 110% B: Adhesive strength holding value is in the range of 80% to less than 90% or over 110% and 120% or less Δ: Adhesive strength retention value is 75% or more and less than 80% or more than 120% and is in a range of 125% or less ×: Adhesive strength retention value is a value less than 75% or 125 % Is over

[Example 2]
In Example 2, with respect to 100 parts by weight of the (meth) acrylic acid ester copolymer as the (A) component, FP-600 is 40 parts by weight as the (B) -1 component, and 25 as the (B) -2 component. A flame retardant pressure-sensitive adhesive tape was prepared and evaluated in the same manner as in Example 1 except that the following compound, which is a kind of condensed aromatic phosphate ester that is solid at ° C, was added to 40 parts by weight. The obtained results are shown in Table 2.
(B) -2 component: 1,3-phenylenebis (dixylenyl) phosphate
(Daihachi Chemical Co., Ltd., PX-200)
Hereinafter, the component (B) -2 may be referred to as PX-200.

[Example 3]
In Example 3, when the component (A) is copolymerized, the proportion of the monomer component (a) is changed to 96 parts by weight, and the proportion of the monomer component (c) is changed to 2 parts by weight. Other than that, a flame-retardant adhesive tape was prepared and evaluated in the same manner as in Example 1. The obtained results are shown in Table 2.

[Example 4]
In Example 4, when the component (A) is copolymerized, the proportion of the monomer component (a) is changed to 88 parts by weight, and the proportion of the monomer component (c) is changed to 10 parts by weight. Other than that, a flame-retardant adhesive tape was prepared and evaluated in the same manner as in Example 1. The obtained results are shown in Table 2.

[Example 5]
In Example 5, when the component (A) is copolymerized, the proportion of the monomer component (a) is changed to 75 parts by weight, and the proportion of the monomer component (c) is changed to 23 parts by weight. Other than that, a flame-retardant adhesive tape was prepared and evaluated in the same manner as in Example 1. The obtained results are shown in Table 2.

[Example 6]
In Example 6, when the component (A) is copolymerized, the proportion of the monomer component (a) is changed to 70 parts by weight, and the proportion of the monomer component (c) is changed to 28 parts by weight. Other than that, a flame-retardant adhesive tape was prepared and evaluated in the same manner as in Example 1. The obtained results are shown in Table 2.

[Example 7]
In Example 7, when the component (A) is copolymerized, the proportion of the monomer component (a) is changed to 63 parts by weight and the proportion of the monomer component (c) is changed to 35 parts by weight. Other than that, a flame-retardant adhesive tape was prepared and evaluated in the same manner as in Example 1. The obtained results are shown in Table 2.

[Example 8]
In Example 8, 80 parts by weight of BA as the monomer component (a), 10 parts by weight of dimethylacrylamide (DMAAm) as the monomer component (c), and 10 parts by weight of HEA as the monomer component (d) And (A) component is polymerized, and the addition amount of component (C) is 0.3 wt.% As solid content with respect to 100 parts by weight of (meth) acrylic acid ester copolymer as component (A). A flame retardant adhesive tape was prepared and evaluated in the same manner as in Example 1 except that the composition was changed to be a part. The obtained results are shown in Table 2.

[Example 9]
In Example 9, a flame retardant adhesive tape was prepared and evaluated in the same manner as in Example 1 except that the monomer component (c) was changed to N-isopropylacrylamide (NIPAAm). The obtained results are shown in Table 2.

[Example 10]
In Example 10, the amount of addition of component (B) was changed to 160 parts by weight with respect to 100 parts by weight of (meth) acrylic acid ester copolymer as component (A). A flame-retardant adhesive tape was prepared and evaluated in the same manner as in 1. The obtained results are shown in Table 2.

[Example 11]
In Example 11, 60 parts by weight of PX-200 as component (B) -1 and 25 parts as component (B) -2 with respect to 100 parts by weight of (meth) acrylic acid ester copolymer as component (A). A flame-retardant pressure-sensitive adhesive tape was prepared and evaluated in the same manner as in Example 1 except that the following compound, which is a kind of non-condensed aromatic phosphate that is liquid at ° C, was added to 30 parts by weight. The obtained results are shown in Table 2.
(B) -2 component: cresyl di 2,6-xylenyl phosphate
(Daihachi Chemical Co., Ltd., PX-110)

[Example 12]
In Example 12, when copolymerizing the (meth) acrylic acid ester copolymer as the component (A), instead of 2 parts by weight of 2-hydroxyethyl acrylate (HEA) as the monomer component (d) A flame retardant adhesive tape was prepared and evaluated in the same manner as in Example 1 except that 2 parts by weight of 4-hydroxybutyl acrylate (HBA) was used. The obtained results are shown in Table 2.

[Comparative Example 1]
In Comparative Example 1, the component (A) was polymerized from 90 parts by weight of BA as the monomer component (a) and 10 parts by weight of acrylic acid (AAc) as the monomer component (b). ) Component (C) -1 as a component is 2.25 parts by weight as a solid content and component (C) -2 is a solid as a component based on 100 parts by weight of a (meth) acrylic acid ester copolymer as a component. A flame retardant adhesive tape was prepared and evaluated in the same manner as in Example 1 except that 0.07 part by weight was added. The obtained results are shown in Table 2.
(C) -1 component: Tolylene diisocyanate crosslinking agent (manufactured by Toyo Ink Manufacturing Co., Ltd., BHS8515, solid content 37.5% by weight)
(C) -2 component: epoxy-based crosslinking agent (manufactured by Soken Chemical Co., Ltd., E-AX, solid content 5% by weight)
In the following, the above-described (C) -1 component and (C) -2 component may be referred to as BHS8515 and E-AX, respectively.

[Comparative Example 2]
In Comparative Example 2, Comparative Example 1 except that PX-200 was added to 30 parts by weight as Component (B) with respect to 100 parts by weight of (meth) acrylic acid ester copolymer as Component (A). In the same manner as above, a flame-retardant adhesive tape was prepared and evaluated. The obtained results are shown in Table 2.

[Comparative Example 3]
In Comparative Example 3, with respect to 100 parts by weight of the (meth) acrylic acid ester copolymer as the (A) component, except that the following compound was added as 30 parts by weight as the (B) component, Similarly, a flame-retardant adhesive tape was prepared and evaluated. The obtained results are shown in Table 2.
Component (B): Phosphazene compound (manufactured by Otsuka Chemical Co., Ltd., SPS-100)
Hereinafter, the component (B) may be referred to as SPS-100.

[Comparative Example 4]
In Comparative Example 4, Example 1 was conducted except that the addition amount of the component (B) was 50 parts by weight with respect to 100 parts by weight of the (meth) acrylic acid ester copolymer as the component (A). A flame retardant adhesive tape was prepared and evaluated in the same manner as described above. The obtained results are shown in Table 2.

[Comparative Example 5]
In Comparative Example 5, when the component (A) is copolymerized, the proportion of the monomer component (a) is changed to 80 parts by weight, and the proportion of the monomer component (b) is changed to 20 parts by weight. Furthermore, Comparative Example except that BHS8515 as component (C) was added to 2.1 parts by weight as solid content with respect to 100 parts by weight of (meth) acrylic acid ester copolymer as component (A) A flame-retardant adhesive tape was prepared and evaluated in the same manner as in 1. The obtained results are shown in Table 2.

[Comparative Example 6]
In Comparative Example 6, when the component (A) is copolymerized, the proportion of the monomer component (a) is changed to 95 parts by weight and the proportion of the monomer component (b) is changed to 5 parts by weight. Furthermore, Comparative Example except that BHS8515 as component (C) was added to 2.25 parts by weight as a solid content with respect to 100 parts by weight of (meth) acrylate copolymer as component (A) A flame-retardant adhesive tape was prepared and evaluated in the same manner as in 1. The obtained results are shown in Table 2.

[Comparative Example 7]
In Comparative Example 7, when the component (A) is copolymerized, the proportion of the monomer component (a) is changed to 98 parts by weight, and the proportion of the monomer component (b) is changed to 2 parts by weight. Other than that, a flame-retardant adhesive tape was prepared and evaluated in the same manner as in Comparative Example 1. The obtained results are shown in Table 2.

[Comparative Example 8]
In Comparative Example 8, a flame-retardant adhesive tape was prepared and evaluated in the same manner as in Example 7 except that the component (B) was not added. The obtained results are shown in Table 2.
In Comparative Example 8, since the initial adhesive strength and the adhesive strength after standing were zipped (vibration phenomenon seen in the adhesive strength measurement chart within a certain range), the average value of the upper and lower limits was used. The adhesive strength retention was calculated considering the initial adhesive strength and the adhesive strength after standing.

[Comparative Example 9]
In Comparative Example 9, Example 7 was carried out except that the amount of component (B) added was 10 parts by weight with respect to 100 parts by weight of (meth) acrylic acid ester copolymer as component (A). A flame retardant adhesive tape was prepared and evaluated in the same manner as described above. The obtained results are shown in Table 2.
In Comparative Example 9 as well, zipping (vibration phenomenon seen in the adhesive strength measurement chart within a certain range) occurred in the initial adhesive strength and the adhesive strength after standing, and therefore the average value of the upper and lower limits was used. The adhesive strength retention was calculated considering the initial adhesive strength and the adhesive strength after standing.

[Comparative Example 10]
In Comparative Example 10, Example 7 was carried out except that the amount of the (B) component added was 30 parts by weight with respect to 100 parts by weight of the (meth) acrylic acid ester copolymer as the (A) component. A flame retardant adhesive tape was prepared and evaluated in the same manner as described above. The obtained results are shown in Table 2.

[Comparative Example 11]
In Comparative Example 11, a flame-retardant adhesive tape was prepared and evaluated in the same manner as in Example 4 except that the component (B) was not added. The obtained results are shown in Table 2.

＊「Ｚ」はジッピング（一定の範囲で粘着力の測定チャートに見られる振動現象）が生じたことを示す。

* “Z” indicates that zipping (vibration phenomenon seen in the measurement chart of adhesive force within a certain range) occurred.

As described above in detail, according to the present invention, a carboxyl group-containing vinyl compound is substantially used as a monomer component constituting the (meth) acrylic acid ester copolymer that is the component (A) as the adhesive main agent. On the other hand, by using a predetermined amount of a nitrogen-containing vinyl compound and containing an aromatic phosphate ester as a flame retardant as the component (B) in a predetermined ratio with respect to the obtained adhesive main agent. For example, even when the pressure-sensitive adhesive composition is left in a high-temperature and high-humidity environment for 7 days, the adhesiveness is effectively suppressed while effectively suppressing hydrolysis of the phosphate ester in the pressure-sensitive adhesive composition. It became possible to improve.
Further, as the flame retardant as the component (B), a predetermined amount of liquid aromatic phosphate ester, a condensed liquid aromatic phosphate ester, or 1,3-phenylenebis (dialkyl) is used. By using specific aromatic phosphates such as silenyl phosphate), bisphenol A bis (diphenyl phosphate) and 1,3-phenylene bis (diphenyl phosphate) For the (meth) acrylic acid ester copolymer that is the derived component (A), it exhibits a predetermined plastic effect and exhibits good adhesive properties and higher flame retardancy in the flame retardant adhesive composition. I was able to do it.
As a result, the flame retardant pressure-sensitive adhesive composition excellent in flame retardancy to satisfy UL94 standard VTM-0 and the like and excellent in adhesive properties, and such a flame retardant pressure-sensitive adhesive composition are used. The flame-retardant pressure-sensitive adhesive tape and the flame-retardant pressure-sensitive adhesive sheet were obtained.
Therefore, the flame-retardant pressure-sensitive adhesive composition of the present invention is remarkably used for, for example, improving the quality of flame-retardant pressure-sensitive adhesive tapes and sheets used for insulating tapes for electronic parts, quality display labels for flameproof articles, and the like. Expected to contribute.

1: coating layer, 2: release film, 10: flame retardant adhesive layer, 100: flame retardant adhesive tape, 101: tape base material, 200: adherend

According to the present invention, a flame retardant pressure-sensitive adhesive composition comprising a (meth) acrylic acid ester copolymer as the component (A) and a flame retardant as the component (B), wherein the component (B) A certain flame retardant contains an aromatic phosphate which is liquid at 25 ° C., and the amount of the flame retardant which is the component (B) is 100 weights of the (meth) acrylic acid ester copolymer which is the component (A). The blending amount of the aromatic phosphate that is liquid at 25 ° C. is 30% by weight or more with respect to the entire flame retardant as the component (B). The following (a)-(c) component is included as a monomer component at the time of copolymerizing the (meth) acrylic acid ester copolymer which is the value of (A) component A flammable adhesive composition is provided to solve the above-mentioned problems. Can.
(A) (meth) acrylic acid alkyl ester having 1 to 12 carbon atoms of alkyl group: 100 parts by weight (b) carboxyl group-containing vinyl compound: 0 part by weight or 0 to 1 part by weight (provided that 0 part by weight is included) Absent.)
(C) Nitrogen-containing vinyl compound: 1 to 70 parts by weight That is, in the case of the flame retardant pressure-sensitive adhesive composition of the present invention, flame retardant is obtained by containing an aromatic phosphate ester as a flame retardant in a predetermined ratio. While maintaining the safety and transparency of the pressure-sensitive adhesive composition, excellent flame retardancy can be obtained.
More specifically, by using a predetermined amount of the liquid aromatic phosphate ester, a phenomenon in which the flame retardant precipitates on the surface of the flame retardant pressure-sensitive adhesive composition while maintaining flame retardancy, so-called blooming occurs. , Can be effectively suppressed.
Further, by using a predetermined amount of such a liquid aromatic phosphate ester, (meth) acrylic acid which is component (A) containing (c) component aromatic ring-containing vinyl compound such as acryloylmorpholine as a structural unit An excellent plasticizing effect can be exerted on the ester copolymer, and the adhesive property in the flame retardant adhesive composition can be further improved.
In addition, as the component (b), a carboxyl group-containing vinyl compound, that is, a vinyl compound having a carboxyl group in the molecule is strictly limited to a predetermined amount or less, and more preferably, it is substantially not used. Due to the catalytic action of the group, the aromatic phosphate ester as a flame retardant hydrolyzes, and as a result, the flame retardancy and tackiness of the flame retardant adhesive composition are reduced over time. Can be suppressed.
Furthermore, since a predetermined amount of a nitrogen-containing vinyl compound, that is, a vinyl compound having a nitrogen atom in the molecule is used as the component (c), good adhesive properties at the initial stage and over time can be obtained.
More specifically, it is considered that the initial tackiness in the flame-retardant pressure-sensitive adhesive composition is usually insufficient by strictly limiting the blending amount of the carboxyl group-containing vinyl compound as the component (b) to a predetermined value or less. However, since a predetermined amount of the nitrogen-containing vinyl compound as component (c) is used, sufficient initial adhesiveness can be obtained, and such adhesiveness can be effectively maintained over time. can do.
In addition, the “flame retardant pressure-sensitive adhesive composition” in the present invention is an uncrosslinked flame retardant pressure-sensitive adhesive composition or a cross-linked flame retardant pressure-sensitive adhesive composition. If it is a flame retardant pressure-sensitive adhesive composition having a composition, it means a broad meaning.

Another aspect of the present invention is a flame retardancy comprising (meth) acrylic acid ester copolymer as component (A) and flame retardant as component (B) on one or both sides of the substrate. A flame retardant pressure-sensitive adhesive tape comprising the pressure-sensitive adhesive composition as a pressure-sensitive adhesive layer, wherein the flame retardant as component (B) contains an aromatic phosphate ester that is liquid at 25 ° C. An amount of a certain flame retardant is 70 to 200 parts by weight with respect to 100 parts by weight of (A) component (meth) acrylate copolymer , and an aromatic that is liquid at 25 ° C. The blending amount of the phosphate ester is set to a value of 30% by weight or more with respect to the whole flame retardant as the component (B), and the (meth) acrylic acid ester copolymer as the component (A) is copolymerized. As monomer components at the time, the following components (a) to (c) are A flame retardant pressure-sensitive adhesive tape according to claim Mukoto.
(A) (meth) acrylic acid alkyl ester having 1 to 12 carbon atoms of alkyl group: 100 parts by weight (b) carboxyl group-containing vinyl compound: 0 part by weight or 0 to 1 part by weight (provided that 0 part by weight is included) Absent.)
(C) Nitrogen-containing vinyl compound: 1 to 70 parts by weight In other words, a flame-retardant adhesive tape not only having excellent adhesiveness but also satisfying a predetermined level of UL94 standard is obtained. In addition, it can be suitably used for applications such as tape for fixing and binding in electronic equipment.

Still another aspect of the present invention is a flame retardant comprising a (meth) acrylic acid ester copolymer as the component (A) and a flame retardant as the component (B) on one or both sides of the substrate. A flame-retardant pressure-sensitive adhesive sheet comprising a pressure-sensitive adhesive composition as a pressure-sensitive adhesive layer, wherein the flame retardant as component (B) contains an aromatic phosphate ester that is liquid at 25 ° C., and component (B) The amount of the flame retardant is a value within the range of 70 to 200 parts by weight with respect to 100 parts by weight of the (meth) acrylic acid ester copolymer as the component (A) , and the fragrance that is liquid at 25 ° C. The blending amount of the group phosphate ester is set to a value of 30% by weight or more with respect to the entire flame retardant as the component (B), and the (meth) acrylic acid ester copolymer as the component (A) is copolymerized. As a monomer component in carrying out, the following (a)-(c) A flame retardant pressure-sensitive adhesive sheet which comprises a minute.
(A) (meth) acrylic acid alkyl ester having 1 to 12 carbon atoms of alkyl group: 100 parts by weight (b) carboxyl group-containing vinyl compound: 0 part by weight or 0 to 1 part by weight (provided that 0 part by weight is included) Absent.)
(C) Nitrogen-containing vinyl compound: 1 to 70 parts by weight That is, since a flame-retardant pressure-sensitive adhesive sheet not only having excellent adhesiveness but also satisfying a predetermined level of UL94 standard is obtained, for example, quality indication of flameproofing articles It can be effectively used for applications such as labels, wallpaper, information display labels for electronic equipment casings or parts.

[First Embodiment]
1st Embodiment of this invention is a flame retardant adhesive composition containing the (meth) acrylic acid ester copolymer as (A) component, and the flame retardant as (B) component, The flame retardant that is component B) contains an aromatic phosphate that is liquid at 25 ° C., and the amount of flame retardant that is component (B) is the amount of (meth) acrylic ester that is component (A). With respect to 100 parts by weight of the polymer, a value within the range of 70 to 200 parts by weight, and the blending amount of the aromatic phosphate ester that is liquid at 25 ° C., with respect to the entire flame retardant as the component (B), The following (a)-(c) component is included as a monomer component at the time of copolymerizing the (meth) acrylic acid ester copolymer which is 30 weight% or more and (A) component. It is the flame-retardant adhesive composition characterized.
(A) (meth) acrylic acid alkyl ester having 1 to 12 carbon atoms of alkyl group: 100 parts by weight (b) carboxyl group-containing vinyl compound: 0 part by weight or 0 to 1 part by weight (provided that 0 part by weight is included) Absent.)
(C) Nitrogen-containing vinyl compound: 1 to 70 parts by weight That is, the first embodiment of the present invention is a flame retardant pressure-sensitive adhesive composition used in the mode illustrated in FIGS. Now, a specific description will be given with reference to the drawings as appropriate.

At least one of the aromatic phosphoric acid ester, liquid aromatic phosphoric acid esters, i.e., is characterized in that an aromatic phosphoric acid ester which is liquid at 25 ° C..
This is because such a liquid aromatic phosphate ester can more effectively suppress the occurrence of blooming.
Examples of the type of aromatic phosphate that is liquid at 25 ° C. include bisphenol A bis (diphenyl phosphate), tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl 2,6-xylate. Examples thereof include nyl phosphate, 2-ethylhexyl diphenyl phosphate, 1,3-phenylenebis (diphenyl phosphate) and the like alone or in combination of two or more.
The viscosity (measured at 25 ° C.) of the liquid aromatic phosphate is preferably 50000 mPa · sec or less, more preferably 10 to 30000 mPa · sec, and more preferably 100 to 25000 mPa · sec. More preferably, the value is within the range of sec.

Moreover, the compounding quantity of liquid aromatic phosphate is made into the value of 30 weight% or more with respect to the whole quantity of the flame retardant which is (B) component, It is characterized by the above-mentioned .
The reason for this is that if the blending amount is less than 30% by weight, it may be difficult to effectively suppress blooming due to the flame retardant.
Further, by using a predetermined amount of such a liquid aromatic phosphate ester, the flame retardant pressure-sensitive adhesive composition exhibits a plastic effect on the nitrogen-containing vinyl compound (c), for example, acryloylmorpholine. This is because the adhesive properties in can be further improved.
Accordingly, the blending amount of the liquid aromatic phosphate ester is more preferably set to a value within the range of 50 to 100% by weight, based on the total amount of the flame retardant as the component (B), and is 70 to 90% by weight. It is more preferable to set the value within the range.

6). Flame-retardant pressure-sensitive adhesive layer The flame-retardant pressure-sensitive adhesive composition can be constituted as a flame-retardant pressure-sensitive adhesive layer through the following steps (1) to (3).
(1) A flame retardant pressure-sensitive adhesive composition comprising a (meth) acrylic acid ester copolymer as the component (A) and a flame retardant as the component (B), which is difficult to be the component (B) The flame retardant contains an aromatic phosphate ester which is liquid at 25 ° C., and the blending amount of the flame retardant which is the component (B) is added to 100 parts by weight of the (meth) acrylic acid ester copolymer which is the component (A). On the other hand, the value is within the range of 70 to 200 parts by weight, and the blending amount of the aromatic phosphate that is liquid at 25 ° C. is a value of 30% by weight or more with respect to the entire flame retardant as the component (B). And the following monomer components (a) to (c) are included as monomer components when copolymerizing the (meth) acrylic acid ester copolymer as component (A): Step of preparing a flame retardant pressure-sensitive adhesive composition (a) Carbon number of alkyl group 1-12 (meth) acrylic acid ester: 100 parts by weight (b) a carboxyl group-containing vinyl compound: 0 parts by weight or 0-1 parts by weight (however, not including 0 parts by weight.)
(C) Nitrogen-containing vinyl compound: 1 to 70 parts by weight (2) Step of applying a flame retardant pressure-sensitive adhesive composition to a substrate to form an application layer (3) Flame retardant pressure-sensitive adhesive composition The step of cross-linking and forming the coating layer as a flame-retardant pressure-sensitive adhesive layer Hereinafter, the steps leading to the construction of the flame-retardant pressure-sensitive adhesive layer will be specifically described with reference to the drawings as appropriate.

(1) Process (1) (Preparation process of a flame-retardant adhesive composition)
Specifically, in the step (1), it is preferable to first copolymerize the monomer components (a) to (c) to obtain a (meth) acrylic acid ester copolymer as the component (A).
The copolymerization method is not particularly limited as long as it is a conventionally known polymerization method, but it is preferable to employ solution polymerization.
Moreover, as a solvent used when performing solution polymerization, what was mentioned as a dilution solvent of the flame-retardant adhesive composition mentioned above can be used, However, It is preferable to use toluene and ethyl acetate especially.
Moreover, it is preferable to add a polymerization initiator when carrying out the copolymerization.
Such a polymerization initiator is not particularly limited as long as it is a conventionally known polymerization initiator, but an azo polymerization initiator is preferably used.
Moreover, the (meth) acrylic acid ester copolymer which is (A) component can be diluted to arbitrary solid content for the purpose of the improvement of the handleability in the process of a process (1) transfer, and workability.
In addition, as a dilution solvent, the dilution solvent mentioned above can be used in the range which does not prevent compatibility with the solution used for solution polymerization.
Next, with respect to the component (A) in the obtained solvent , an aromatic phosphate ester that is liquid at 25 ° C. as a flame retardant that is the component (B), a crosslinking agent that is the component (C), and the like It is preferable to obtain a solution of the flame retardant pressure-sensitive adhesive composition.

[Second Embodiment]
The second embodiment of the present invention comprises a flame retardant comprising a (meth) acrylic acid ester copolymer as the component (A) and a flame retardant as the component (B) on one or both sides of the substrate. A flame retardant pressure-sensitive adhesive tape comprising the pressure-sensitive adhesive composition as a pressure-sensitive adhesive layer, wherein the flame retardant as component (B) contains an aromatic phosphate ester that is liquid at 25 ° C. An amount of a certain flame retardant is 70 to 200 parts by weight with respect to 100 parts by weight of (A) component (meth) acrylate copolymer , and an aromatic that is liquid at 25 ° C. The blending amount of the phosphate ester is set to a value of 30% by weight or more with respect to the whole flame retardant as the component (B), and the (meth) acrylic ester copolymer as the component (A) is copolymerized. As monomer components at the time, the following components (a) to (c) are A flame retardant pressure-sensitive adhesive tape according to claim Mukoto.
(A) (meth) acrylic acid alkyl ester having 1 to 12 carbon atoms of alkyl group: 100 parts by weight (b) carboxyl group-containing vinyl compound: 0 part by weight or 0 to 1 part by weight (provided that 0 part by weight is included) Absent.)
(C) Nitrogen-containing vinyl compound: 1 to 70 parts by weight Hereinafter, the second embodiment of the present invention will be specifically described with reference to FIG. 1 with a focus on differences from the first embodiment.

[Third Embodiment]
The third embodiment of the present invention comprises a flame retardant containing (meth) acrylic acid ester copolymer as component (A) and a flame retardant as component (B) on one or both sides of the substrate. A flame-retardant pressure-sensitive adhesive sheet comprising the pressure-sensitive adhesive composition as a pressure-sensitive adhesive layer, wherein the flame retardant as the component (B) contains an aromatic phosphate ester that is liquid at 25 ° C, and the component (B) An amount of a certain flame retardant is 70 to 200 parts by weight with respect to 100 parts by weight of (A) component (meth) acrylate copolymer , and an aromatic that is liquid at 25 ° C. The blending amount of the phosphate ester is set to a value of 30% by weight or more with respect to the whole flame retardant as the component (B), and the (meth) acrylic acid ester copolymer as the component (A) is copolymerized. As monomer components at the time, the following components (a) to (c) are A flame retardant pressure-sensitive adhesive sheet according to claim Mukoto.
(A) (meth) acrylic acid alkyl ester having 1 to 12 carbon atoms of alkyl group: 100 parts by weight (b) carboxyl group-containing vinyl compound: 0 part by weight or 0 to 1 part by weight (provided that 0 part by weight is included) Absent.)
(C) Nitrogen-containing vinyl compound: 1 to 70 parts by weight Hereinafter, the third embodiment of the present invention will be specifically described focusing on differences from the first and second embodiments.

As described above in detail, according to the present invention, a carboxyl group-containing vinyl compound is substantially used as a monomer component constituting the (meth) acrylic acid ester copolymer that is the component (A) as the adhesive main agent. On the other hand, while using a predetermined amount of a nitrogen-containing vinyl compound, a predetermined proportion of an aromatic phosphate ester that is liquid at 25 ° C. as a flame retardant as the component (B) with respect to the obtained adhesive main component By, for example, even when the pressure-sensitive adhesive composition is left in a high-temperature and high-humidity environment for 7 days, while effectively suppressing hydrolysis of the phosphate ester in the pressure-sensitive adhesive composition, The adhesiveness can be effectively improved.
Further, as the flame retardant as the component (B), a predetermined amount of liquid aromatic phosphate ester, a condensed liquid aromatic phosphate ester, or 1,3-phenylenebis (dialkyl) is used. By using specific aromatic phosphates such as silenyl phosphate), bisphenol A bis (diphenyl phosphate) and 1,3-phenylene bis (diphenyl phosphate) For the (meth) acrylic acid ester copolymer that is the derived component (A), it exhibits a predetermined plastic effect and exhibits good adhesive properties and higher flame retardancy in the flame retardant adhesive composition. I was able to do it.
As a result, the flame retardant pressure-sensitive adhesive composition excellent in flame retardancy to satisfy UL94 standard VTM-0 and the like and excellent in adhesive properties, and such a flame retardant pressure-sensitive adhesive composition are used. The flame-retardant pressure-sensitive adhesive tape and the flame-retardant pressure-sensitive adhesive sheet were obtained.
Therefore, the flame-retardant pressure-sensitive adhesive composition of the present invention is remarkably used for, for example, improving the quality of flame-retardant pressure-sensitive adhesive tapes and sheets used for insulating tapes for electronic parts, quality display labels for flameproof articles, and the like. Expected to contribute.

Claims (10)

(A) A flame retardant pressure-sensitive adhesive composition comprising a (meth) acrylic acid ester copolymer as a component and a flame retardant as a component (B),
The flame retardant as the component (B) contains an aromatic phosphate ester,
The blending amount of the flame retardant as the component (B) is set to a value within the range of 70 to 200 parts by weight with respect to 100 parts by weight of the (meth) acrylic acid ester copolymer as the component (A), and ,
The flame retardant pressure-sensitive adhesive composition comprising the following components (a) to (c) as monomer components when copolymerizing the (meth) acrylic acid ester copolymer as the component (A): object.
(A) (meth) acrylic acid alkyl ester having 1 to 12 carbon atoms of alkyl group: 100 parts by weight (b) carboxyl group-containing vinyl compound: 0 part by weight or 0 to 1 part by weight (provided that 0 part by weight is included) Absent.)
(C) Nitrogen-containing vinyl compound: 1 to 70 parts by weight   The flame-retardant pressure-sensitive adhesive composition according to claim 1, wherein the nitrogen-containing vinyl compound as the component (c) is a vinyl compound having an amide structure in the molecule.   The flame retardant pressure-sensitive adhesive composition according to claim 2, wherein the vinyl compound having an amide structure in the molecule is a (meth) acrylamide derivative.   At least one of the aromatic phosphate esters is an aromatic phosphate ester that is liquid at 25 ° C., and the blending amount of the aromatic phosphate ester that is liquid at 25 ° C. is the component (B) The flame-retardant pressure-sensitive adhesive composition according to any one of claims 1 to 3, wherein the flame-retardant pressure-sensitive adhesive composition has a value of 30% by weight or more with respect to a certain flame retardant.   The flame retardant pressure-sensitive adhesive composition according to claim 4, wherein the aromatic phosphate ester that is liquid at 25 ° C is a condensed aromatic phosphate ester.   The nitrogen-containing vinyl compound as the component (c) is acryloylmorpholine, and the flame retardant as the component (B) is 1,3-phenylenebis (dixylenyl phosphate), bisphenol A bis (diphenyl phosphate). ) And 1,3-phenylenebis (diphenyl phosphate). The flame retardant pressure-sensitive adhesive composition according to any one of claims 1 to 5, wherein   As a further monomer component (d) when copolymerizing the (meth) acrylic acid ester copolymer as the component (A), a hydroxyl group-containing vinyl compound is used with respect to 100 parts by weight of the monomer component (a). The flame retardant pressure-sensitive adhesive composition according to any one of claims 1 to 6, wherein the flame retardant pressure-sensitive adhesive composition is blended at a value within a range of 1 to 15 parts by weight.   The flame retardant pressure-sensitive adhesive according to any one of claims 1 to 7, comprising a crosslinking agent for the (meth) acrylic acid ester copolymer as the component (A) as the component (C). Composition. A flame retardant pressure-sensitive adhesive composition containing (meth) acrylic acid ester copolymer as component (A) and flame retardant as component (B) is provided as a pressure-sensitive adhesive layer on one or both sides of the substrate. Flame retardant adhesive tape,
The flame retardant as the component (B) contains an aromatic phosphate ester,
The blending amount of the flame retardant as the component (B) is set to a value within the range of 70 to 200 parts by weight with respect to 100 parts by weight of the (meth) acrylic acid ester copolymer as the component (A), and ,
A flame-retardant pressure-sensitive adhesive tape comprising the following components (a) to (c) as monomer components for copolymerizing the (meth) acrylic acid ester copolymer as the component (A).
(A) (meth) acrylic acid alkyl ester having 1 to 12 carbon atoms of alkyl group: 100 parts by weight (b) carboxyl group-containing vinyl compound: 0 part by weight or 0 to 1 part by weight (provided that 0 part by weight is included) Absent.)
(C) Nitrogen-containing vinyl compound: 1 to 70 parts by weight A flame retardant pressure-sensitive adhesive composition containing (meth) acrylic acid ester copolymer as component (A) and flame retardant as component (B) is provided as a pressure-sensitive adhesive layer on one or both sides of the substrate. Flame retardant adhesive sheet,
The flame retardant as the component (B) contains an aromatic phosphate ester,
The blending amount of the flame retardant as the component (B) is set to a value within the range of 70 to 200 parts by weight with respect to 100 parts by weight of the (meth) acrylic acid ester copolymer as the component (A), and ,
A flame-retardant pressure-sensitive adhesive sheet comprising the following components (a) to (c) as monomer components for copolymerizing the (meth) acrylic acid ester copolymer as the component (A).
(A) (meth) acrylic acid alkyl ester having 1 to 12 carbon atoms of alkyl group: 100 parts by weight (b) carboxyl group-containing vinyl compound: 0 part by weight or 0 to 1 part by weight (provided that 0 part by weight is included) Absent.)
(C) Nitrogen-containing vinyl compound: 1 to 70 parts by weight

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