TWI405784B - Polymeric dispersant and pigment composition thereof - Google Patents

Abstract

Polymeric dispersant and pigment composition thereof are provided. The polymeric dispersant comprises the reaction product of a compound with amine end group and a diisocyanate via polymerization, wherein the compound with amine end group comprises diamine compounds triamind compounds of combinations thereof.

Description

Polymer type dispersant and pigment composition containing the same

This invention relates to a dispersant, and more particularly to a polymeric dispersant.

Organic pigments are different from dyes. They are insoluble solid particles. They are dispersed in different solvents or resins and then applied. They have better thermal stability, durability and UV resistance. Brightness, etc., and can protect the surface of the coated system. It can be seen from the above that the pigment is superior to the dye in all aspects, but because the pigment particles are easy to aggregate during the production process, and the particle size is large, the pigment particles are too large, resulting in a decrease in the amount of the pigment, color saturation, color saturation and stability. dispersion. Therefore, the dispersant is further used to promote fine dispersion, nanocrystallization, and high stability of the pigment particles. Currently, the color paste dispersion used in liquid crystal display (LCD) color filters requires dispersion and stability, and requires high light transmittance and good color resistivity resolution. However, the key is to dispersant, and the dispersant must be targeted. The anchoring system design anchoring end can have a strong adsorption of pigment, and the solvation end should have a proper solvation effect.

Many of the past polymeric dispersants used radom copolymers, but these are relatively ineffective materials. U.S. Patent No. 5,852,123 discloses a dispersant comprising a graft copolymer having a backbone of a polymer and a megamonomer side chain grafted onto the backbone and connecting the megamonomer or the polar group on the backbone, designed to Adsorbed on the surface of the pigment particles and attached to the copolymer dispersant on the surface of the pigment. However, such dispersants cause the pigment particles to come too close together and cause the stability and rheology of the pigment dispersion and the coating to deteriorate, and to reduce the strength of the color.

Based on the above, a new dispersant is designed to optimize the dispersion of the pigment, which is the focus of the dispersant technology.

The present invention provides a dispersing agent which is a compound having a terminal amine group (for example, poly(oxyalkylene) diamine or poly(oxyalkylene) triamine) and diisocyanate ( Diisocyanate) (a compound having two isocyanate compounds) is a polymer-type dispersant which is synthesized as a dispersant or a stabilizer to form a stable pigment composition (dispersion or color paste). The dispersant also includes a urea-based (Urea) segment which can be hydrogen bonded to a functional group modified by the surface of the pigment, attached to the outer layer of the pigment, and further comprising an oil-soluble segment. (for example, oxypropylene segment), the oleophilic nature of the segment can be utilized to dissolve the dispersant in the acrylic monomer solvent and stabilize the pigment particles dispersed in the acrylic by the steric hindrance effect of the dispersing agent In the monomer, the aggregation of the pigment is avoided, the dispersant can be added to a high concentration, and the resulting dispersion can be maintained at a low viscosity.

According to a preferred embodiment of the present invention, the polymeric dispersant may be obtained by polymerizing a compound having a terminal amine group with a diisocyanate, wherein the compound having a terminal amine group comprises a diamine. (diamine) a compound, a triamine compound, or a mixture thereof.

According to another preferred embodiment of the present invention, the present invention also provides a pigment composition comprising: a pigment; and a polymeric dispersant comprising a compound having a terminal amine group and a diisocyanate The diisocyanate is obtained by polymerization, wherein the compound having a terminal amine group comprises a diamine compound, a triamine, or a mixture thereof.

The method, features, and advantages of the invention are further illustrated by the following examples, which are not intended to limit the scope of the invention.

The polymer type dispersant of the present invention is obtained by polymerizing a compound having a terminal amino group and a diisocyanate. Wherein, the compound having a terminal amine group may comprise a diamine compound, a triamine compound, or a mixture thereof (diamine and triamine compounds simultaneously participate in polymerization). The polymerization temperature of the terminal amine group-containing compound and the diisocyanate may be room temperature (25-30 ° C), or may be below room temperature (for example, 0-25 ° C), wherein the terminal amine group The molar ratio of the compound to the diisocyanate is from 2:1 to 5:4. Further, the compound having a terminal amine group may further comprise a monoamine compound in addition to a diamine compound, a triamine compound, or a mixture thereof, and a polymerization reaction with the diisocyanate.

The diisocyanate may comprise 4,4-methylene bis phenyl diisocyanate (MDI), toluene diisocyanate (TDI), isophorone diisocyanate (IPDI), Or a mixture thereof.

The diamine compound may comprise a polyether diamine, or an olefin diamine, such as polyoxypropylene diamine, polyoxyethylene diamine, poly(ethyl ether-propyl ether) (poly(oxyethylene-oxypropylene) diamine), or a mixture thereof. In addition, the diamine compound can also be

Wherein the X, Y, and Z systems are greater than or equal to 1, and the R is independently hydrogen, methyl, or ethyl. The diamine compound may have a molecular weight of between 200 and 4000 g/mol.

The triamine compound may comprise a polyether triamine, or an olefin triamine, such as a polyoxypropylene triamine. In a preferred embodiment of the invention, the triamine compound comprises Wherein the X, Y, and Z systems are greater than or equal to 1, and the R is independently hydrogen, methyl, or ethyl. The triamine compound may have a molecular weight of between 400 and 5000 g/mol.

In addition, the above monoamine may comprise

Wherein the X, Y, and Z systems are greater than or equal to 1, and the R is independently hydrogen, methyl, or ethyl.

The compound having a terminal amine group (monoamine, diamine, or triamine polymer) used in the present invention may also be a commercially available product such as a series of amines sold by Huntsman Chemical Co. Base compounds such as Jeffamine D2000 [poly(propylene glycol bis(2-amino propyl ether), Mw 2000], Jeffamine D4000 [polypropylene glycol bis(2-aminopropyl) (poly(propylene glycol) bis(2-amino propyl ether), Mw 4000] and Jeffamine ED2001 [(polypropylene glycol block-polyethylene glycol block-polypropylene glycol block) bis(2-aminopropyl) (poly(propylene glycol)-block-poly(ethylene glycol)-block-poly(propylene glycol) bis(2-aminopropyl ether), Mw 2000]; others such as T3000 [trifunctional polypropylene glycol 2-amino Tri-functional poly(propylene glycol 2-amino propyl ether), Mw 3000], T5000 [tri-functional poly(propylene glycol 2-aminopropyl ether), Mw 5000] and so on. The structural series of the Jeffamine series are as follows:

Further, according to a preferred embodiment of the present invention, the present invention also provides a pigment composition comprising: a pigment; and the above-mentioned polymer type dispersant. Wherein the pigment can be a green pigment. The content of the polymeric dispersant may be not less than 10% by weight based on the solid content of the pigment composition.

Hereinafter, the polymer type dispersant of the present invention and the pigment composition containing the same will be described by way of the following examples to further clarify the technical features of the present invention.

Preparation of polymeric dispersant Example 1

Poly(oxypropylene) diamine (Poly(oxypropylene) diamine, Jeffamine amine POP2000, molecular weight 2000) was placed in a vacuum oven at 100 ° C for 8 hours to remove water, and diphenylmethane diisocyanate (4,4 ' -Methylenebis (phenyl isocyanate, MDI) was purified by distillation under reduced pressure. MDI (2 g, 8 mmol) was placed in a four-necked flask, and 20 g of Toluene (about 10 times that of MDI) was added to dissolve, followed by mechanical stirring to dissolve the MDI under nitrogen. The solution was in a homogeneous state. Next, 32 g of POP2000 (dissolved in 150 g of Toluene) was added to the MDI solution once, and the product was collected by reacting for 10 minutes under nitrogen at room temperature. In this example, POP2000 and MDI were collected. The ratio of the ears is 2: 1. The product is poured on an aluminum pan or a glass plate, and placed in a circulating oven at 80 ° C to remove Toluene, to obtain the product POP2000-MDI (A) (linear polymer), which is a pale yellow viscous liquid. The polymerization reaction process is as shown in the reaction formula (I):

Example 2-4

The method described in Example 1 was carried out, but the molar ratio of POP2000 to MDI was adjusted from 2:1 to 3:2, 4:3, and 5:4, respectively, to obtain the product POP2000-MDI(B)-( D).

Table 1 lists the molar ratios of POP2000 to MDI used in Examples 1-4, and the resulting product.

Example 5

MDI (2 g, 8 mmol) was placed in a four-necked flask, and 20 g of Toluene (about 10 times that of MDI) was added to dissolve, followed by mechanical stirring to dissolve the MDI under nitrogen to bring the solution to a homogeneous state. Next, 16 g of POP2000 and 3.2 g of POP400 (poly(oxypropylene) diamine, Jeffamine amine POP400, molecular weight 400) were dissolved in 38 g of Toluene, added to the MDI solution once, and reacted for 10 minutes under nitrogen at room temperature. The product can be collected. In this example, the molar ratio of polypropyl ether diamine (POP2000 and POP400 total) to MDI is 2:1, and the molar ratio of POP2000 to POP400 is 1:1. The product was poured on an aluminum pan or a glass plate, and placed in a circulating oven at 80 ° C to remove Toluene, to obtain the product POP2000-POP400-MDI (A) (linear polymer), which was a pale yellow viscous liquid.

Example 6-9

The method described in Example 1 was carried out, but the molar ratio of POP2000 to POP400 was adjusted from 1:1 to 7:1, 3:1, 5:3, and 3:5, respectively, to obtain the product POP2000-POP400- MDI(B)-(E). The molar ratio of polypropyl ether diamine (total of POP2000 and POP400) to MDI was still maintained at 2:1.

Table 2 lists the molar ratios of POP2000 & POP400 to MDI used in Examples 5-9, the molar ratio of POP2000 to POP400, and the obtained product.

Example 10

MDI (2 g, 8 mmol) was placed in a four-necked flask, dissolved in 20 g of Toluene, and then mechanically stirred until the MDI was dissolved under nitrogen to bring the solution to a homogeneous state. Next, take 29.1 g of POP2000 (dissolved in 150 g of Toluene) and 0.6 g of T403 (polyoxypropylene triamine, Jeffamine amine T403, molecular weight 440) dissolved in 28 g of Toluene, once added to the MDI solution, under nitrogen and at room temperature. The reaction was carried out for ten minutes to collect the product. In this example, the molar ratio of polyetheramine (POP2000 and T403) to MDI was 2:1, and the molar ratio of POP2000 to T403 was 10:1. On the aluminum plate or glass plate, placed in a circulating oven at 80 ° C to remove Toluene, the product POP2000-T403-MDI (A) (dendrimer) can be obtained as a light yellow viscous liquid. The above polymerization process is as follows: II):

Example 11-12

The method described in Example 10 was carried out, but the molar ratio of POP2000 to T403 was adjusted from 10:1 to 15:1 and 30:1, respectively, to obtain the product POP2000-T403-MDI(B)-(C). . The molar ratio of polyetheramine (total of POP2000 and T403) to MDI was still maintained at 2:1.

Table 3 lists the molar ratios of POP2000 and T403 used in Examples 10-12, the molar ratio of polyetheramine (total of POP2000 and T403) to MDI, and the obtained product.

Example 13-15

The method described in Example 10 was carried out, but the molar ratio of polyetheramine (POP2000 and T403 total) to MDI was adjusted from 2:1 to 3:2, 4:3 and 5:4, respectively. POP2000-T403-MDI(D)-(F). The molar ratio of POP2000 to T403 is still maintained at 10:1.

Table 4 lists the molar ratios of POP2000 and T403 used in Examples 10 and 13-15, the molar ratio of polyetheramine (total of POP2000 and T403) to MDI, and the obtained product.

Yan Preparation of material composition Example 15

1 g of POP2000-MDI (A) (dispersant obtained in Example 1) was dissolved in 17 g of HDDA (1,6 hexanediol diacrylate), placed in a plastic grinding bottle, and then 2 g of green pigment and 1.0 mm of zirconium were added. Beads 70g. Next, it was ground by a mechanical stirrer at a number of revolutions of 2000 rpm for 20 minutes to obtain a pigment composition (A). Finally, the obtained pigment dispersion solution (A) was analyzed for viscosity and molecular particle size, and the results are shown in Table 5.

Comparative Example 1

This was carried out as described in Example 15, but without adding any dispersant, to obtain a pigment composition (B). The obtained pigment dispersion solution (B) was analyzed for viscosity and molecular particle diameter, and the results are shown in Table 5.

Example 16-29

This was carried out as described in Example 15, except that the dispersant used was replaced by POP2000-MDI (A) with POP2000-MDI(B)-(D), POP2000-POP400-MDI(A)-(D). And POP2000-T403-MDI (A)-(F), respectively, the pigment compositions (C)-(O) were obtained. The obtained pigment dispersion solution (C)-(O) was analyzed for viscosity and molecular particle diameter, and the results are shown in Table 5.

As can be seen from Table 5, the pigment composition to which the dispersant of the present invention is added has a significantly lower viscosity than the pigment composition to which the dispersant of the present invention is not added, and in addition, the diameter of the pigment composition can also be Use different dispersants to regulate.

In summary, the present invention provides a dispersing agent which is composed of a compound having a terminal amine group (for example, poly(oxyalkylene) diamine or poly(oxyalkylene) triamine) and A polymeric dispersant prepared by the reaction of a diisocyanate (a compound having two isocyanate functional groups), which can be used as a dispersing agent or a stabilizer to form a stable pigment composition (dispersion liquid) The dispersing agent comprises an oil-soluble segment (for example, an oxypropylene segment), and the oleophilic property of the segment (as a salvation segment) can be utilized to dissolve the dispersing agent in the acrylic monomer solvent. Further, the dispersing agent also contains a Urea segment (as an anchoring point) which can be hydrogen bonded to a functional group modified by the surface of the pigment to attach and stabilize the pigment particles. Pigment aggregation can be avoided and can be added to high concentrations (>10% by weight) and the resulting dispersion can remain at low viscosity.

Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention, and the present invention may be modified and modified without departing from the spirit and scope of the invention. The scope is subject to the definition of the scope of the patent application attached.

Claims (28)

A polymeric dispersant obtained by polymerizing a compound having a terminal amine group and a diisocyanate, wherein the compound having a terminal amine group comprises two diamine compounds Or a diamine compound and a triamine compound. The polymeric dispersant according to claim 1, wherein the molar ratio of the compound having a terminal amino group to the diisocyanate is from 2:1 to 5:4. The polymeric dispersing agent according to claim 1, wherein the diamine compound comprises a polyether diamine or an olefin diamine. The polymeric dispersing agent according to claim 1, wherein the triamine compound comprises a polyether triamine or an olefin triamine. The polymeric dispersant according to claim 1, wherein the diisocyanate comprises 4,4-methylene bis phenyl diisocyanate (MDI), toluene diisocyanate (toluene diisocyanate, TDI), isophorone diisocyanate (IPDI), or a mixture thereof. The polymeric dispersing agent according to claim 1, wherein the diamine compound comprises polyoxypropylene diamine, polyoxyethylene diamine, poly(ethyl) Poly(oxyethylene-oxypropylene) diamine, or a mixture thereof. The polymeric dispersing agent according to claim 1, wherein the diamine compound comprises ,or Wherein the X, Y, and Z systems are greater than or equal to 1, and the R is independently hydrogen, methyl, or ethyl. The polymeric dispersing agent according to claim 1, wherein the diamine compound has a molecular weight of 200 to 4000 g/mol. The polymeric dispersing agent according to claim 1, wherein the triamine compound is a polyoxypropylene triamine. The polymeric dispersing agent according to claim 1, wherein the triamine compound comprises Wherein the X, Y, and Z systems are greater than or equal to 1, and the R is independently hydrogen, methyl, or ethyl. The polymeric dispersing agent according to claim 1, wherein the triamine compound has a molecular weight of 400 to 5000 g/mol. The polymeric dispersing agent according to claim 1, wherein the compound having a terminal amine group further comprises a monoamine compound. The polymeric dispersant according to claim 12, wherein the monoamine comprises ,or Wherein the X, Y, and Z systems are greater than or equal to 1, and the R is independently hydrogen, methyl, or ethyl. A pigment composition comprising: a pigment; and the polymeric dispersant according to claim 1 of the patent application. The pigment composition of claim 14, wherein the molar ratio of the compound having a terminal amine group to the diisocyanate is 2:1. Until 5:4. The pigment composition of claim 14, wherein the diamine compound comprises a polyether diamine, or an olefin diamine. The pigment composition of claim 14, wherein the triamine compound comprises a polyether triamine, or an olefin triamine. The pigment composition of claim 14, wherein the diisocyanate comprises 4,4-methylene bis phenyl diisocyanate (MDI), toluene diisocyanate (TDI) , isophorone diisocyanate (IPDI), or a mixture thereof. The pigment composition of claim 14, wherein the diamine compound comprises polyoxypropylene diamine, polyoxyethylene diamine, poly(ethyl ether- Poly(oxyethylene-oxypropylene) diamine, or a mixture thereof. The pigment composition of claim 14, wherein the diamine compound comprises ,or Wherein the X, Y, and Z systems are greater than or equal to 1, and the R is independently hydrogen, methyl, or ethyl. The pigment composition of claim 14, wherein the diamine compound has a molecular weight of from 200 to 4000 g/mol. The pigment composition of claim 14, wherein the triamine compound is a polyoxypropylene triamine. The pigment composition of claim 14, wherein the triamine compound comprises Wherein the X, Y, and Z systems are greater than or equal to 1, and the R is independently hydrogen, methyl, or ethyl. The pigment composition of claim 14, wherein the triamine compound has a molecular weight of from 400 to 5000 g/mol. The pigment composition of claim 14, wherein the compound having a terminal amine group further comprises a monoamine compound. Things. The pigment composition of claim 25, wherein the monoamine comprises ,or Wherein the X, Y, and Z systems are greater than or equal to 1, and the R is independently hydrogen, methyl, or ethyl. The pigment composition of claim 14, wherein the pigment is a green pigment. The pigment composition according to claim 14, wherein the polymer dispersant is contained in an amount of not less than 10% by weight based on the solid content of the pigment composition.