JP6319793B2 - Composite resin composition and method for producing the same - Google Patents

Description

  The present invention relates to a composite resin composition containing a urethane resin having a phosphate ester structure and a (meth) acrylic resin, and a method for producing the same.

In the field of coating agents and fiber resin processing agents used for various metals, plastics, and paper substrates, urethane-acrylic composite resin compositions are known as coating compositions having high adhesion to substrates.
By the way, this coating composition is required to have flame retardancy depending on the usage scene. As a method of imparting flame retardancy, a method of adding a flame retardant such as a halogen series, a phosphorus series, or a metal hydroxide to a resin is known. However, these methods may cause problems such as bleed out of the flame retardant and plasticization of the resin by the flame retardant.

  For these problems, a method for imparting flame retardancy by bonding a flame retardant component to a resin has been studied. For example, a urethane-acrylic composite resin composition (Patent Document 1) obtained by copolymerizing an acrylic composition with a phosphorus-containing monomer is known as such a flame retardant resin. Moreover, as a phosphorus-containing urethane resin composition, a composition using a phosphorus-containing polyol as a part of a polyol constituting urethane (Patent Document 2) is known.

JP 2005-54146 A JP 2003-104581 A

  However, the urethane-acrylic composite resin described in Patent Document 1 is considered not to have sufficient flame retardancy. This is because the content of phosphorus is relatively small, so that flame retardancy is not sufficiently exhibited, and a phosphorus-containing monomer is copolymerized with an acrylic component. It is considered that the orientation of the resin is localized and localized on the surface when the coating film is formed because it becomes a urethane resin into which phosphorus has not been introduced, and therefore it is difficult to express flame retardancy.

  Further, Patent Document 2 describes the flame retardancy of a urethane resin, but this resin is made of a urethane resin alone, and sufficient coating film durability may not be obtained. This is because the urethane resin itself has a relatively low molecular weight, and it is necessary to form a cross-linked structure by using a reinforcing agent (epoxysilane), etc., and it is necessary to improve durability. End up.

  Then, this invention aims at obtaining the urethane-acrylic composite resin composition which has sufficient coating-film durability and a flame retardance. Another object of the present invention is to provide a method for producing this urethane-acrylic composite resin composition and an aqueous resin dispersion.

  The present inventors have made extensive studies in view of the above-mentioned problems. By introducing a phosphoric ester structure into the urethane composition of the urethane-acrylic composite resin, sufficient coating film durability and flame retardancy can be obtained. As a result, the present invention has been completed. That is, the gist of the present invention resides in the following [1] to [9].

[1] It comprises the following components (A) and (B), and the weight ratio of the components (A) and (B) [weight of the component (A)] / [weight of the component (B)] is 20/80. A composite resin composition of ~ 90/10.
Component (A): Urethane resin shown in <1> below .
Component (B): (meth) acrylic resin .
<1> Urethane resin obtained by reacting the component (A) with polyisocyanate (a-1) and polyol (a-2) containing polyol (a-3) represented by the following formula (1) .

（前記式（１）中、Ｒ^１〜Ｒ^８は互いに異なっていてもよく、水素原子、炭素数１〜１２の炭化水素基又はハロゲン元素から選ばれる基であり、Ｒ^９は水素原子、炭素数１〜１０のアルキル基、フェニル基又はフェノキシ基であり、Ｘはそれぞれ独立して直接結合、炭素数１〜１３の２価の炭化水素基、−Ｏ−、−Ｓ−、−ＳＯ_２−及び−ＣＯ−から選ばれる基であり、ｎは１〜２０の自然数である。）

(In the formula (1), R ^{1 to} R ⁸ may be different from each other, and are a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms, or a group selected from halogen elements, and R ⁹ is a hydrogen atom, carbon. C 1 -C 10 alkyl, phenyl or phenoxy group, X is independently a direct bond, a divalent hydrocarbon group having 1 to 13 carbon atoms, -O -, - S -, - SO 2 - And -CO-, and n is a natural number of 1 to 20.)

[2] The component (A), the polyisocyanate (a-1), by reacting a polyol containing a polyol having at least the polyol (a-3) and a carboxyl group (a-4) (a- 2) The composite resin composition according to [ 1 ], which is obtained in the above manner.

（式（３）中、Ｒ^１４は炭素数１〜４のアルキル基である。） [3] before Kipo triol (a-4) is a compound represented by the following formula (3), the composite resin composition according to [2].

(In formula (3), R ¹⁴ is an alkyl group having 1 to 4 carbon atoms.)

（式（４）中、Ｒ^１５は水素原子又はメチル基であり、Ｒ^１６は炭素数１〜１２のアルキル基、グリシジル基又はホスホン酸アルキル基である。） [ 4 ] The composite resin according to any one of [1] to [ 3 ], wherein the component (B) is obtained by polymerizing a (meth) acrylic monomer represented by the following formula (4): Composition.

(In the formula ^{(4), R 15} is a hydrogen atom or a methyl ^{group, R 16} is an alkyl group, a glycidyl group or a phosphonic acid alkyl group having 1 to 12 carbon atoms.)

[ 5 ] An aqueous dispersion obtained by dispersing the composite resin composition according to any one of [1] to [ 4 ] in water.
[ 6 ] A method for producing a composite resin composition according to any one of [1] to [ 4 ], wherein the component (A) is a constituent component of the component (B). The manufacturing method of the composite resin composition which emulsion-polymerizes this (meth) acrylic-type monomer (b-1) in the state with which the monomer (b-1) was mixed.

  The urethane-acrylic composite resin composition of the present invention and the aqueous resin dispersion obtained using the composition are excellent in coating film durability and flame retardancy. For this reason, the urethane-acrylic composite resin composition of the present invention can be suitably used for applications such as coating agents for metals and plastics, resin processing agents for paper and fibers, and the like.

The composite resin composition according to the present invention is referred to as a urethane resin having a phosphate ester structure (hereinafter referred to as “component (A)”) and a (meth) acrylic resin (hereinafter referred to as “component (B)”). ) In a predetermined ratio. This composite resin composition may be in the form of an aqueous dispersion dispersed in water.
The urethane-acrylic composite resin composition of the present invention comprises the following component (A) and component (B), and the weight ratio of component (A) to component (B) [weight of component (A)] / [component ( The weight of B) is 20/80 to 90/10.
Component (A): Urethane resin obtained by reacting polyisocyanate (a-1) shown below and polyol (a-2) containing polyol (a-3) Component (B): (meth) acrylic resin

The urethane-acrylic composite resin composition of this invention has the effect of being excellent in coating film durability and flame retardancy. The excellent coating film durability is considered to result from the composite of urethane resin and acrylic resin, and the excellent flame retardancy is the phosphate ester structure or phosphonic acid in the following urethane resin. It is thought to be due to the ester structure .

[Component (A)]
The urethane resin of component (A) are those generally obtained by reacting a polyisocyanate (a-1) and polyol containing a port polyol (a-3) (a- 2).

  Examples of the polyisocyanate (a-1) include organic polyisocyanates such as various aliphatic polyisocyanates, alicyclic polyisocyanates, and aromatic polyisocyanates. Specific examples of these polyisocyanates include dicyclohexylmethane diisocyanate, 1,6-hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, 1,3-cyclohexylene diisocyanate, 1,4-cyclohexylene diisocyanate, 2,4 -Tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate and the like.

The polyol (a-3) is a compound having a phosphate ester group or a phosphonate ester group and a plurality of hydroxyl groups. This polyol (a-3) is a compound represented by the following formula (1) or a compound represented by the following formula (2) , and in the urethane synthesis, the reactivity is likely to proceed relatively well. preferable.

In the formula (1), R ^{1 to} R ⁸ may be different from each other and are a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms, or a group selected from a halogen element, and R ⁹ is a hydrogen atom or carbon number. 1 to 10 alkyl group, phenyl group or phenoxy group, X is independently a direct bond, a divalent hydrocarbon group having 1 to 13 carbon atoms, —O—, —S—, —SO ₂ — and It is a group selected from -CO-, and n is a natural number of 1-20.

In the above formula ^{(2), R 11} is an alkyl group or an N of 1 to 4 carbon atoms, N- bis (hydroxyalkyl) group (number of carbon atoms in the hydroxyalkyl group is 1 to ^{4.), R 12} and R <^13> is respectively independently a C1-C4 alkyl group.

Among the compounds represented by the formula (1), R ^{1 to} R ⁸ may be different from each other and are preferably groups selected from a hydrogen atom, a methyl group, and a halogen element. R ⁹ is preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group or a phenoxy group. R ^{1 to} R ⁸ and R ⁹ having such a structure are preferable from the viewpoint of improving flame retardancy and water resistance, and specific examples of such compounds include the following formula (5 ).

Among the compounds represented by the formula (2), R ¹² and R ¹³ are the same, and R ¹¹ is an N, N-bis (hydroxyalkyl) group (the hydroxyalkyl group has 1 to 4 carbon atoms). The compound represented by (6) is more preferable from the viewpoint of imparting hydrophilicity to the urethane composition and from the viewpoint of reactivity. Specific examples of such a compound include the compound represented by the following (6).

  The polyol (a-4) having a carboxyl group is not particularly limited as long as it is a polyol having a carboxylic acid group, and examples thereof include a compound represented by the following formula (3).

In the formula (3), R ¹⁴ is an alkyl group having 1 to 4 carbon atoms.

  Examples of such compounds include dimethylol alkanoic acids such as dimethylolpropionic acid, dimethylolbutanoic acid, and dimethylolhexanoic acid.

  Examples of other polyols include ethylene glycol, propylene glycol, 1,3-propane polyol, 1,3-butane polyol, 1,4-butane polyol, 1,5-pentane polyol, and 3-methyl-1,5-pentane. Polyol, 1,6-hexane polyol, neopentyl glycol, diethylene glycol, trimethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, cyclohexane dimethanol, methylpentane polyol adipate, polyester polyol, polyether polyol And carbonate group-containing polyols.

[Component (B)]
The vinyl polymer constituting the component (B) refers to a monomer having a vinyl group, that is, a polymer of a radical polymerizable monomer. In particular, it is more preferable to use a radically polymerizable monomer that does not contain active hydrogen, since it is difficult to consume an isocyanate that is not intended.

  The radical polymerizable monomer may be a monofunctional unsaturated monomer having only one vinyl group as a functional group, or a polyfunctional unsaturated monomer having two or more vinyl groups as a functional group. Good. Further, a mixture of a polyfunctional unsaturated monomer and a monofunctional unsaturated monomer may be used.

  Examples of the monofunctional unsaturated monomer include (meth) acrylic monomers, vinyl halide compounds, aromatic vinyl compounds and the like as shown in the following formula (4). In this specification, “(meth) acryl” means “acryl or methacryl”.

In the formula (4), R ¹⁵ is a hydrogen atom or a methyl group, and R ¹⁶ is an alkyl group having 1 to 12 carbon atoms, a glycidyl group, or an phosphonic acid alkyl group.

  The (meth) acrylic monomer refers to an ester compound of (meth) acrylic acid, (meth) acrylic acid alkyl ester, (meth) acrylic acid glycidyl, (meth) acrylic acid diphenyloxyethyl phosphate, ( Examples thereof include diethyl methacrylic acid diethyloxyethyl phosphate. In the polymerization, one of them may be used, or a mixture of two or more thereof may be used.

  Examples of the (meth) acrylic acid alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, T-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, (meth) acrylic Examples include tridecyl acid, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, and the like.

  Examples of the polyfunctional unsaturated monomer include ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate. , Hexanediol di (meth) acrylate, nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, allyl (meth) acrylate, etc., divinylbenzene, divinylnaphthalene and Examples thereof include aromatic divinyl compounds such as derivatives thereof.

Further, in addition to the above, N, N-divinylaniline, divinyl ether, divinyl sulfide, divinyl sulfone, and compounds having three or more vinyl groups can be mentioned.
In addition, the monomer which has the said vinyl group may be used independently, and 2 or more types may be mixed and used for it.

  The component (B) is obtained by polymerizing the radical polymerizable monomer, and the upper limit of the glass transition temperature (Tg) of the component (B) is preferably 80 ° C., and preferably 70 ° C. It is preferable for the glass transition temperature to be 80 ° C. or lower because the resulting coating film does not become too hard and it is easy to prevent the occurrence of cracks. On the other hand, the lower limit of the glass transition temperature (Tg) is preferably 20 ° C, and preferably 30 ° C. It is preferable for the glass transition temperature to be 20 ° C. or higher because adhesion is easily improved.

[Production of composite resin composition]
Next, the urethane-acrylic composite resin composition production method according to the present invention will be described in detail.
In this production method, the (meth) acrylic monomer (b) is mixed with the component (A) and the (meth) acrylic monomer (b-1) which is a component of the component (B). -1) is a production method for emulsion polymerization, and specific examples include the production methods shown in the following first production method to third production method.

Specifically, the first manufacturing method, first, (meth) polyol having a carboxyl group in the presence, before Kipo triol (a-3), and optionally acrylic monomer (b-1) and (a-4) polyols containing (a-2), by reacting a polyisocyanate (a-1), to produce a urethane resin (component (a)).

  In the above production process, the urethane reaction is carried out in the presence of a radical polymerizable monomer, so that the viscosity during the reaction can be kept low, and the reaction can proceed uniformly.

Before the content of Kipo triol (a-3) is the polyol (a-2) the total amount, good or 50.0 wt%, preferably at least 65.0 wt%. Since it is easy to express a flame retardance as it is more than the said lower limit, it is preferable. On the other hand, the upper limit of the content is preferably 95.0% by weight, and preferably 92.0% by weight. It is preferable for it to be not more than the above upper limit value because the viscosity at the time of urethane reaction does not become too high and the water dispersibility is hardly lowered.

  When using the said polyol (a-4) which has a carboxyl group, this content is good to 5.0 weight% or more with respect to polyol (a-2) whole quantity, and 7.0 weight% or more is preferable. It is preferable for it to be not less than the above lower limit value because the water dispersibility of the resin is unlikely to deteriorate and poor dispersion is unlikely to occur. On the other hand, the upper limit of the content is preferably 25.0% by weight, and preferably 20.0% by weight. It is preferable for it to be not more than the above upper limit value because the water resistance of the coating film is unlikely to decrease.

The mixing ratio of the polyisocyanate (a-1) and the polyol (a-2) may be (a-1) / (a-2) = 1.1 / 1 to 2.5 / 1 in weight ratio. Preferably, 1.2 / 1 to 2.0 / 1 is more preferable. By setting the ratio between the two within the above range, the viscosity increase during the reaction can be reduced, the reaction can be performed stably, and the residual amount of unreacted isocyanate can be suppressed, and the reaction product can be stabilized over time. Property is improved.

The mixing amount of the (meth) acrylic monomer (b-1) is 20/80 when the weight ratio of the component (A) to the component (B) in the resulting composite resin composition is (A) / (B). It is essential that the amount is as described above. If the weight ratio is smaller than 20/80, the amount of the urethane resin as the component (A) becomes too small, and it may be difficult to develop flame retardancy. From the viewpoint of facilitating the expression of flame retardancy, (A) / (B) is preferably 30/70 or more. On the other hand, the upper limit of the weight ratio of (A) to component (B) is required to be an amount such that (A) / (B) is 90/10. When the weight ratio is smaller than 90/10, when the urethane reaction is performed in the (meth) acrylic monomer, the viscosity at the time of the reaction becomes excessively high and it becomes difficult to perform the reaction uniformly. There is. From the viewpoint of further improving this point, (A) / (B) is preferably 80/20 or less.

  Next, when a urethane group obtained by the above polymerization contains a carboxyl group, it is neutralized with a basic compound. Thereby, the obtained aqueous dispersion is further stabilized.

  The basic compound is not particularly limited as long as it can neutralize the carboxyl group, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, trimethylamine, triethylamine, tributylamine, triethanolamine and the like And tertiary amines.

  Subsequently, water is added and the liquid mixture of the said urethane resin and a radically polymerizable monomer is disperse | distributed in water, and an aqueous dispersion liquid is obtained. Subsequently, the (meth) acrylic monomer (b-1) is emulsion-polymerized to obtain a (meth) acrylic polymer, thereby producing an aqueous dispersion of a urethane-acrylic composite resin composition.

  The amount of water used to obtain the aqueous dispersion is not particularly limited, but is preferably 0.5 to 9 times by weight, more preferably 1 to 4 times by weight with respect to the neutralized solution. If it is not more than the above upper limit value, the resin content does not decrease too much, and a thick coating tends to be easily obtained. On the other hand, when it is at least the lower limit, the viscosity at the time of water dispersion does not become too high, which is preferable from the viewpoint of handleability.

  In the step of obtaining the aqueous dispersion by adding water, an emulsifier is used as necessary. Examples of the emulsifier include ionic surfactants such as anionic, cationic and amphoteric, nonionic surfactants, and the like.

  In the emulsion polymerization step, emulsion polymerization is usually performed by adding a polymerization initiator. As this polymerization initiator, a polymerization initiator used in usual emulsion polymerization can be used. Examples of the polymerization initiator include persulfates such as ammonium persulfate, potassium persulfate, and sodium persulfate, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvalero). Nitrile) and other azo compounds, hydrogen peroxide, hydroperoxides such as t-butyl hydroperoxide, radical polymerization initiators such as peroxides such as benzoyl peroxide and lauroyl peroxide, and these are independent. Or 2 or more types can be mixed and used. Further, these radical polymerization initiators can be used as a redox polymerization initiator in combination with a reducing agent such as sodium sulfite, sodium hydrogen sulfite, sodium thiosulfate, tartaric acid, L-ascorbic acid, thiourea dioxide and the like. .

  It is preferable that the polymerization temperature of the emulsion polymerization is usually about 50 to 100 ° C., and the reaction time is usually about 2 to 16 hours.

  Next, as the second production method, first, urethanization of the component (a-2) including the component (a-1) and the component (a-3) in the presence of a part of the component (b-1). There is a production method in which the reaction is carried out, and then the remaining component (b-1) is added to neutralize the composition corresponding to the component (b-1), followed by water dispersion and then emulsion polymerization.

  Furthermore, as the third production method, first, in the presence of the component (b-1) other than the specific component (GMA, AN, diphenyl-2-methacryloyloxyethyl phosphate (the following chemical formula 7)), (a-1 ) And urethanization of component (a-2) including component (a-3), neutralize and then water-disperse, and then emulsion polymerization is performed after the remaining specific component is added and absorbed. There are methods.

  The content of each component in the second production method and the third production method can be the same as the content of each component in the first production method. In the second production method, the content of a part of the component (b-1) used first is preferably 20 to 95% by weight, and preferably 30 to 90% by weight, based on the entire component (b-1). By satisfying this range, when performing the urethane reaction in the component (b-1) to be used first, the viscosity during the reaction does not become too high, and the effect that the reaction can be performed uniformly can be achieved. .

  The content of phosphorus contained in the composite resin composition thus obtained is preferably 2.5% by weight or more based on the total solid content of the components (A) and (B) in the composite resin composition, 3.0 weight% or more is preferable. It is preferable from a viewpoint of making it easier to express a flame retardance as it is more than the said lower limit. On the other hand, the upper limit of the phosphorus content is preferably 6.5% by weight, and preferably 6.0% by weight. It is preferable from the viewpoint of avoiding the problem that the viscosity during the reaction becomes too high and it becomes difficult to carry out the reaction uniformly when the urethane reaction is carried out at the upper limit or less.

  The composite resin composition thus obtained can have a structure in which an acrylic composition is emulsified with a urethane composition to form a composite in the particle, and the urethane composition is necessarily in a form localized on the particle surface. Thus, the phosphorus component can be localized on the resin surface.

The aqueous dispersion of the composite resin composition thus obtained can be used as various coating agents and resin processing agents, and is particularly excellent in adhesion to polar substrates, and the formed coating film and processed product are flame retardant. It is possible to give a function of having a property.
For example, by applying this composite resin composition as a back coating agent to a fiber base material and processing the fiber, it can be usefully used as a backing agent for flame retardant car mats and car seats.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example, this invention is not limited by a following example, unless the summary is exceeded. First, the evaluation method and the raw materials used will be described.

(Evaluation method)
[Combustion test]
It implemented according to UL94 vertical combustion test. The test piece was prepared by impregnating glass cloth with various resins at 30% by weight and drying at room temperature overnight. Thereafter, the strips were cut into strips having a length of 125 mm and a width of 13 mm, 8 sheets were stacked, and a test piece was prepared by applying a load of 0.23 kg / cm ^{2 in} a dryer at 120 ° C. for 6 hours.
Using the obtained test piece, a UL94 vertical combustion test was carried out, and the average combustion time was obtained by measuring the total of the first and second burning times as the burning time of each test piece four times. .
Furthermore, evaluation was performed according to the following criteria.
A: The longest combustion time is 10 seconds or less (corresponding to V-0).
○ The longest combustion time exceeds 10 seconds and is 30 seconds or less (corresponding to V-1).
Δ: The longest combustion time exceeds 30 seconds and is 60 seconds or less.
X: The longest burning time exceeds 60 seconds.

[Water resistance test]
A coating solution in which 6 wt% of NMP (N-methyl-2-pyrrolidone) was added to each sample was prepared, applied at 100 g / m ² on a glass plate degreased with alcohol, and dried at room temperature for 3 days as a test piece. did. The prepared test piece was immersed in room temperature water for 60 minutes, pulled up from the water, and lightly rubbed the coating film with a finger to visually observe the state. The water resistance was evaluated according to the following criteria.
○: The coating film retained as a film.
(Triangle | delta): The thing in which the coating film collapsed.
X: The coating film collapsed when pulled up from water.

[Isopropyl alcohol resistance (IPA resistance) test]
Using a test piece similar to the above water resistance test, drop 1 drop of IPA on the coating surface with a dropper, visually observe the coating surface state after 2 minutes, and lightly press the surface with a finger to tack the coating surface It was confirmed. IPA resistance was evaluated according to the following criteria.
A: No change in the coating surface state, no tack when pressed with a finger, and no pressed mark left.
○: Slightly tacky.
(Triangle | delta): The change was confirmed to the coating-film surface state.
X: The coating film surface state was not changed, and dissolution of the coating film was confirmed when pressed with a finger, and the pressed state did not return.

(raw materials)
[Po polyol (a-3)]
Nofia (registered trademark) OL1001 (trade name): manufactured by FRX Polymers, a compound corresponding to the formula (1) (R ^{1 to} R ⁸ are hydrogen atoms, R ⁹ is a methyl group, and X is —C (CH ₃ ) ₂ —), weight average molecular weight (Mw): 2,000 to 3,000 (catalog value), solid content 100% by weight, phosphorus content 9.1% by weight, hydroxyl value 88 mgKOH / g, hereinafter referred to as “OL1001”.

[Polyol having carboxyl group (a-4)]
Dimethylolpropionic acid: manufactured by Perstorp Specialty Chemicals AB, hereinafter referred to as “DPMA”.

[Other polyols]
Polycarbonate polyol: Daicel Chemical Industries, Ltd .: Plaxel CD220, hydroxyl value 56.7 mgKOH / g, hereinafter referred to as “CD220”.
Polytetramethylene glycol: manufactured by Mitsubishi Chemical Corporation: PTMG1000, hydroxyl value 111.1 mgKOH / g, hereinafter referred to as “PTMG1000”.

[Polyisocyanate (a-1)]
Isophorone diisocyanate: manufactured by Evonik Degussa: VESTANAT IPDI (trade name), hereinafter referred to as “IPDI”.
Hexamethylene diisocyanate: Showa Chemical Co., Ltd .: Reagent, hereinafter referred to as “HDI”.

[Basic compounds]
Triethylamine: Wako Pure Chemical Industries, Ltd .: Reagent, hereinafter referred to as “TEA”.
[Chain extender]
-3% by weight hydrazine aqueous solution: MG Otsuka Chemical Co., Ltd .: 80% hydrated hydrazine (trade name) adjusted with ion-exchanged water so that the hydrazine content is 3% by weight, hereinafter referred to as "HD" Called.

[(Meth) acrylic monomer (b-1)]
Methyl methacrylate: Mitsubishi Rayon Co., Ltd .: Acryester M (trade name), hereinafter referred to as “MMA”.
・ Butyl acrylate: manufactured by Mitsubishi Chemical Corporation, hereinafter referred to as “BA”.
-Glycidyl methacrylate: Mitsubishi Gas Chemical Co., Inc., hereinafter referred to as “GMA”.
Acrylonitrile: manufactured by Dianitricks Co., Ltd. Hereinafter referred to as “AN”.
[Other monomers]
Phosphorus-containing monomer: diphenyl-2-methacryloyloxyethyl phosphate, manufactured by Daihachi Chemical Industry Co., Ltd .: hereinafter referred to as “MR-260”. This chemical formula is shown in (7) below.
This compound can be used to increase the phosphorus content and is incorporated into the composite resin composition as a reactive monomer.

[Polymerization initiator]
Redox initiator: 7 wt% t-butyl hydroperoxide aqueous solution (manufactured by Kayaku Akzo Co., Ltd .: 70 wt% t-butyl hydroperoxide aqueous solution adjusted to 7 wt% with water, hereinafter “t -BHP ") and a 1 wt% ascorbic acid aqueous solution (manufactured by BASF Japan Ltd .: ascorbic acid dissolved in ion exchange water at a concentration of 1 wt%, hereinafter referred to as" AsA "). It was.

[solvent]
Cyclohexanone: manufactured by Ube Industries, Ltd. (hereinafter referred to as “CHN”)
[emulsifier]
-ADEKA rear soap SR-10 ... made by ADEKA, [({[alpha]-[2- (allyloxy) -1-({[alkyl (C = 10-14)] oxy} methyl) ethyl]-[omega] -hydroxypoly ( n = 1 to 100) (oxyethylene)} as the main component, the oxirane weight of {alkanol (C = 10-14, branched type) and 1- (allyloxy) -2,3-epoxypropane reaction product} Ammonium salt of the sulfated product of the adduct], hereinafter referred to as “SR-10”.

[Flame retardants]
Phosphorus flame retardant: manufactured by Daihachi Chemical Industry Co., Ltd .: DAIGUARD880, aliphatic condensed phosphate ester, phosphorus content: 14.8% by weight, hereinafter referred to as “DAIGUARD880”.

Thermometer, a four-neck flask equipped with a stirrer and reflux condenser, 44.6 g of OL1001 as Po polyol (a-3), the DMPA as the polyol (a-4) having a carboxyl group 4.7 g, ( As the (meth) acrylic monomer (b-1), 20.8 g of MMA and 20.8 g of BA were weighed and heated and stirred at 70 ° C. in a mixed gas atmosphere of nitrogen and air to dissolve OL1001. Thereafter, 20 g of IPDI was added as polyisocyanate (a-1) and stirred at 90 ° C. for 5 hours to obtain an isocyanate group-terminated prepolymer.

The temperature in the flask was lowered to 60 ° C., 52.0 g of MR-260 was added as a phosphorus-containing monomer, and after confirming that it was uniform, 3.5 g of TEA was added to neutralize the carboxylic acid, and GMA Was added and mixed uniformly. Then added over about 15 minutes of deionized water 235.7G, cause phase inversion emulsification to obtain an emulsified dispersion of the (meth) acrylic monomer urethane prepolymer as emulsifying component.

Order to further the urethane prepolymer for polymerization, the internal temperature of the flask 3 wt% aqueous solution of hydrazine as a chain extender (HD) after the addition of 16.7g was heated to 50 ° C., of a radical initiator t- After adding 14.9 g of BHP and stirring for 1 minute, 52 g of an AsA aqueous solution was added to polymerize the (meth) acrylic monomer. After the increase in the internal temperature was observed by the polymerization reaction, the internal temperature was adjusted to 70 ° C., the aging reaction was carried out for 2 hours, and then cooled to obtain an emulsion of a composite resin composition of urethane resin and acrylic resin . The emulsion of the obtained composite resin composition was subjected to a combustion test, a water resistance test, and an IPA resistance test. The results are shown in Table-1.

[Example 2]
From Example 1, as the other polyol, 12.0 g of polycarbonate polyol CD220 was used, and the urethane resin was synthesized by the same synthesis method as in Example 1 except that the amount of raw material used was changed as shown in Table 1. An emulsion of a composite resin composition with an acrylic resin was obtained. The emulsion of the obtained composite resin composition was subjected to a combustion test, a water resistance test, and an IPA resistance test. The results are shown in Table-1.

[Example 3]
A composite resin composition of urethane resin and acrylic resin by the same synthesis method as in Example 1 except that PTMG1000 was used as the other polyol from Example 1 and the amount of raw material used was changed as shown in Table 1. A product emulsion was obtained. The emulsion of the obtained composite resin composition was subjected to a combustion test, a water resistance test, and an IPA resistance test. The results are shown in Table-1.

[Examples 4 and 5]
From Example 3, an emulsion of a composite resin composition of a urethane resin and an acrylic resin was obtained by the same synthesis method as in Example 1 with the respective raw material amounts shown in Table 1 except that the phosphorus-containing monomer MR260 was not used. It was. The emulsion of the obtained composite resin composition was subjected to a combustion test, a water resistance test, and an IPA resistance test. The results are shown in Table-1.

[Example 6]
From Examples 4 and 5, HDI was used in combination as polyisocyanate (a-1), and the urethane resin and acrylic resin were synthesized by the same synthesis method as in Example 1 except that the amount of raw materials used was changed as shown in Table 1. An emulsion of the composite resin composition was obtained. The emulsion of the obtained composite resin composition was subjected to a combustion test, a water resistance test, and an IPA resistance test. The results are shown in Table-1.

[Example 7]
From Examples 4 and 5, the monomer AN was used in combination, and the composite resin composition of urethane resin and acrylic resin was obtained by the same synthesis method as in Example 1 except that the amount of raw materials used was changed as shown in Table 1. A product emulsion was obtained. The emulsion of the obtained composite resin composition was subjected to a combustion test, a water resistance test, and an IPA resistance test. The results are shown in Table-1.

[Example 8]
From Example 4, the monomer resin GMA was not used, and the composite resin composition of urethane resin and acrylic resin was synthesized by the same synthesis method as in Example 1 except that the amount of raw material used was changed as shown in Table 1. An emulsion was obtained. The emulsion of the obtained composite resin composition was subjected to a combustion test, a water resistance test, and an IPA resistance test. The results are shown in Table-1.

[Example 9]
40.2g of phosphorus flame retardant DAIGUARD880 was added to the composite resin composition obtained in Example 4 and mixed by stirring to obtain an emulsion of the composite resin composition containing the flame retardant. The emulsion of the obtained composite resin composition was subjected to a combustion test, a water resistance test, and an IPA resistance test. The results are shown in Table-2.

[Example 10]
In the same manner as in Example 8, 34.5 g of DAIGUARD880 was added to the composite resin composition obtained in Example 5 and mixed with stirring to obtain an emulsion of the composite resin composition containing a flame retardant. The emulsion of the obtained composite resin composition was subjected to a combustion test, a water resistance test, and an IPA resistance test. The results are shown in Table-2.

[Comparative Example 1]
In a four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser, weigh 61.3 g of PTMG1000, 6.3 g of DMPA as a carboxylic acid-containing polyol, 29.3 g of MMA, and 29.3 g of BA. The mixture was heated and stirred at 70 ° C. in a mixed gas atmosphere, 30 g of IPDI was added, and the mixture was stirred at 90 ° C. for 4 hours to obtain an isocyanate group-terminated prepolymer.
The temperature in the flask was lowered to 60 ° C., 4.8 g of TEA was added to neutralize the carboxylic acid, and 6.5 g of GMA was added and mixed uniformly. Thereafter, 234.4 g of ion-exchanged water was added over about 15 minutes to perform phase inversion emulsification, and an emulsified dispersion of (meth) acrylic monomer was obtained using a urethane prepolymer as an emulsifying component.
Further, to increase the molecular weight of the urethane prepolymer, 22.5 g of a 3% by weight hydrazine (HD) aqueous solution was added as a chain extender, and then the temperature inside the flask was raised to 50 ° C. to obtain a radical initiator t-BHP9. After adding 3 g and stirring for 1 minute, 33 g of AsA was added to polymerize the (meth) acrylic monomer. After the increase in the internal temperature was observed by the polymerization reaction, the internal temperature was adjusted to 70 ° C., the aging reaction was carried out for 2 hours, and then cooled to obtain an emulsion of a composite resin composition of urethane resin and acrylic resin . The emulsion of the obtained composite resin composition was subjected to a combustion test, a water resistance test, and an IPA resistance test. The results are shown in Table-3.

[Comparative Example 2]
From Comparative Example 1, 22.3 g of CD220 was used instead of PTMG1000, 6.9 g of DMPA, 10.8 g of MMA, and 10.8 g of BA were weighed, and heated and stirred at 70 ° C. in a mixed gas atmosphere of nitrogen and air. Then, 25 g of IPDI was added and stirred at 90 ° C. for 4 hours to obtain an isocyanate group-terminated prepolymer.
The temperature inside the flask was cooled to 70 ° C., 81.2 g of OL1001 as a phosphorus-containing polyol and 27.1 g of MR-260 as a phosphorus-containing monomer were added and dissolved, the temperature inside the flask was lowered to 60 ° C., and 5.2 g of TEA was added. The carboxylic acid is neutralized, and 5.4 g of GMA is added and mixed uniformly. Thereafter, 264.2 g of ion-exchanged water was added over about 15 minutes, and phase-inversion emulsification was performed to obtain an emulsified dispersion of a (meth) acrylic monomer and a phosphorus-containing polyol using a urethane prepolymer as an emulsifying component.
Furthermore, to increase the molecular weight of the urethane prepolymer, 51 g of a 3% by weight hydrazine aqueous solution (HD) was added as a chain extender, the temperature inside the flask was raised to 50 ° C., and acrylic was prepared using the catalysts listed in Table-3. Polymerization was performed to obtain an emulsion of a composite resin composition of urethane resin and acrylic resin mixed with phosphorus-containing polyol. The emulsion of the obtained composite resin composition was subjected to a combustion test, a water resistance test, and an IPA resistance test. The results are shown in Table-3.

[Comparative Example 3]
From the comparative example 2, the emulsion of the composite resin composition of the urethane resin and acrylic resin which mixed the phosphorus containing polyol by the synthesis method similar to the comparative example 2 in each raw material amount shown in Table-3 was obtained. The emulsion of the obtained composite resin composition was subjected to a combustion test, a water resistance test, and an IPA resistance test. The results are shown in Table-3.

[Comparative Example 4]
In a four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser, weigh 103.3 g of OL1001 as a phosphorus-containing polyol, 10.2 g of PTMG1000, 9.5 g of DMPA, 72 g of CHN as a solvent, nitrogen gas The OL1001 was dissolved by heating and stirring to 70 ° C. under an atmosphere. Thereafter, 45 g of IPDI was added and stirred at 90 ° C. for 5 hours to obtain an isocyanate group-terminated prepolymer. The temperature inside the flask was lowered to 60 ° C., 7.2 g of triethylamine was added to neutralize the carboxylic acid, 273.9 g of ion exchange water was added over about 15 minutes, and a urethane prepolymer was phase-inverted and emulsified. Got. Further, 33.8 g of 3% by weight hydrazine aqueous solution (HD) was added as a chain extender to increase the molecular weight of the urethane prepolymer to obtain a phosphorus-containing urethane resin. About the obtained phosphorus containing urethane resin, the combustion test, the water resistance test, and the IPA resistance test were implemented. The results are shown in Table-3.

[Comparative Example 5]
To a four-necked flask equipped with a thermometer, a stirrer and a reflux condenser, add 207.5 g of ion-exchanged water, 3 g of SR-10 as an emulsifier, 45 g of MMA, 45 g of BA, and 10 g of GMA. Emulsify. While stirring, the temperature in the flask was adjusted to 50 ° C., 7.1 g of radical initiator t-BHP was added, and after stirring for 1 minute, 24.8 g of AsA was added to polymerize the (meth) acrylic monomer. After an increase in internal temperature was observed by the polymerization reaction, the internal temperature was adjusted to 70 ° C., an aging reaction was carried out for 2 hours, and then cooled to obtain an acrylic resin emulsion. The resulting acrylic resin emulsion emulsion was subjected to a combustion test, a water resistance test, and an IPA resistance test. The results are shown in Table-3.

[Evaluation of results]
As can be seen from Tables 1 and 2, Examples 1 to 10 corresponding to the composite resin composition of the present invention were excellent in flame retardancy, water resistance and IPA resistance. On the other hand, as can be seen from Table-3, Comparative Examples 1 to 3 and 5 which do not contain a phosphoric ester structure or a phosphonic ester structure and do not contain the component (A) in the present invention are flame retardant, water resistant, One of the IPA characteristics was bad. Moreover, the comparative example 4 which does not contain the component (B) in this invention was bad in IPA resistance.

Claims (6)

It consists of the following component (A) and component (B), and the weight ratio of component (A) to component (B) [weight of component (A)] / [weight of component (B)] is 20/80 to 90 / A composite resin composition which is 10.
Component (A): Urethane resin shown in <1> below .
Component (B): (meth) acrylic resin .
<1> Urethane resin obtained by reacting the component (A) with polyisocyanate (a-1) and polyol (a-2) containing polyol (a-3) represented by the following formula (1) .

(In the formula (1), R ^{1 to} R ⁸ may be different from each other, and are a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms, or a group selected from halogen elements, and R ⁹ is a hydrogen atom, carbon. C 1 -C 10 alkyl, phenyl or phenoxy group, X is independently a direct bond, a divalent hydrocarbon group having 1 to 13 carbon atoms, -O -, - S -, - SO 2 - And -CO-, and n is a natural number of 1 to 20.) Wherein component (A) and the polyisocyanate (a-1), obtained by reacting a polyol containing a polyol having at least the polyol (a-3) and a carboxyl group (a-4) (a- 2) those, composite resin composition according to claim 1. Before Kipo triol (a-4) is a compound represented by the following formula (3), the composite resin composition according to claim 2.

(In formula (3), R ¹⁴ is an alkyl group having 1 to 4 carbon atoms.) The composite resin composition according to any one of claims 1 to 3 , wherein the component (B) is obtained by polymerizing a (meth) acrylic monomer represented by the following formula (4).

(In the formula ^{(4), R 15} is a hydrogen atom or a methyl ^{group, R 16} is an alkyl group, a glycidyl group or a phosphonic acid alkyl group having 1 to 12 carbon atoms.) The aqueous dispersion formed by disperse | distributing the composite resin composition of any one of Claims 1-4 in water. It is a manufacturing method of the composite resin composition of any one of Claims 1-4 ,
The (meth) acrylic monomer (b-1) is emulsified in a state where the component (A) and the (meth) acrylic monomer (b-1) which is a constituent component of the component (B) are mixed. A method for producing a composite resin composition to be polymerized.